JPH06234803A - Production of polymer - Google Patents

Abstract

PURPOSE:To readily and efficiently obtain a polymer having OH groups at both terminals from a wide range of vinylic monomers at a low cost by polymerizing the vinylic monomers in the presence of an initiator consisting essentially of an organic peroxide, alcohols and a specific compound. CONSTITUTION:(A) A vinylic monomer is polymerized in the presence of (B) alcohols (preferably ethylene glycol, pentaerythritol, etc.) by using (C) an initiator system consisting essentially of an organic peroxide (preferably cyclohexanone peroxide or benzoyl peroxide). In the process, (D) a nonphosphorus-based inorganic acid (preferably hydrochloric acid, sulfuric acid, etc.) is further used to carry out the reaction without using components other than the components (A) to (D). Furthermore, the component (B) is preferably used so as to provide (1:10) to (10:1) weight ratio of the components (B):(A) and its molar amount of >=50 times based on the component (C). The component (C) is preferably used in an amount of 0.1-20wt.% based on the component (A) and the component (D) is preferably used in an amount of 0.05-10wt.% based on the amount of the whole components.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polymer having hydroxyl groups at both ends.

[0002]

2. Description of the Related Art A polymer having hydroxyl groups at both terminals is prepared by reacting the hydroxyl groups at the above terminals by an appropriate method.
It can be easily converted to another functional group, and the reactivity of the hydroxyl group at the terminal is utilized to linearize and / or network by reacting the hydroxyl group by an appropriate method, and as a result, The polymer compound has various excellent physical properties such as strength, heat resistance, weather resistance, and durability.

This polymer having hydroxyl groups at both ends is
By exhibiting the characteristic of having hydroxyl groups at both ends, for example, the following great advantages are obtained. When used as various resin raw materials (crosslinking agent etc.) such as polyester resin, polyurethane resin, polycarbonate resin,
Since there are no unreacted substances that impair the physical properties of the material, it is ensured that all polymers are incorporated into the resin crosslinked structure.

A polymer in which a functional group is introduced into a side chain by copolymerizing a vinyl-based monomer having a functional group such as a hydroxyl group, a carboxyl group and an amino group (hereinafter, referred to as a functional group-containing vinyl-based monomer copolymer). When a polymer is used for the reaction, the end thereof becomes a play part (free end) that is not incorporated in the resin (crosslinking) structure, but in a polymer having hydroxyl groups at both ends, Nothing happens.

Since the variation in the distance between the functional groups is extremely small as compared with the vinyl monomer copolymer containing a functional group, the distance between the reaction points (crosslinking points) becomes almost constant, and a uniform resin (crosslinking) structure is formed. to make. For the functional group-containing vinyl monomer copolymer, one having an average number of functional groups of 2.0 was prepared.
Even if an attempt is made to synthesize a thermoplastic polymer by reacting it with a functional chain extender, a trifunctional or higher functional polymer is statistically included due to the synthetic method. It is not possible to synthesize a thermoplastic polymer as a functional polymer, but it does not contain a tri- or higher functional polymer.
With a polymer having hydroxyl groups at both ends, a chain-extended thermoplastic polymer can be easily synthesized.

Further, in the case of a polymer having hydroxyl groups at both ends and at least two hydroxyl groups at at least one end, it has hydroxyl groups at both ends, but only one at that end. As compared with a polymer having only one hydroxyl group, the crosslink density is increased, so that the physical strength of the crosslinked body can be improved, and due to the synergistic effect of the terminal OH groups,
The advantage that the reactivity of the terminal OH group can be improved is recognized.

It has a hydroxyl group at both ends, and
When a polymer having at least two hydroxyl groups at at least one terminal is used, it is an expensive trifunctional compound required for curing a polymer having only one hydroxyl group at the terminal in thermosetting resin applications. It is not necessary to add an NCO compound or a trifunctional or higher functional polyol having poor handleability. Polymers having hydroxyl groups at both ends are used as raw materials or additives for various resins such as polyester resins, polyurethane resins and polycarbonate resins, and various resins such as various block polymers, or by utilizing the above advantages. In addition, paints (high solids, low temperature curing, etc.), elastic wall materials, waterproof coating materials, adhesives, floor materials, tackifiers, adhesives, binders (magnetic recording media, ink binders, casting binders, baked bricks) Binder, graft material, microcapsule, glass fiber sizing, etc.), sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV / EB curable resin, thermosetting elastomer, microcellular, fiber processing agent, plastic Agent, sound absorbing material, damping material, surfactant, gel coating agent,
Resin for artificial marble, impact resistance additive for artificial marble, resin for ink, film (laminate adhesive, protective film, etc.), resin for laminated glass, reactive diluent, various molding materials, elastic fiber, artificial leather, synthetic It is very useful for leather, dispersants, aqueous urethane emulsions, etc.

Conventionally, as the hydroxyl group-containing polymer used in the above-mentioned applications, a vinyl monomer copolymer having a hydroxyl group in the side chain, a polyether group having a hydroxyl group at the terminal,
Examples thereof include polyester, polybutadiene, and polycarbonate. First, a copolymer of vinyl monomers having a hydroxyl group in the side chain is a random radical of a monomer having a hydroxyl group and a monomer having no hydroxyl group. Since it is produced by polymerization, it is difficult to suppress the by-product of copolymers that do not have hydroxyl groups, and in order to avoid this, it is necessary to increase the hydroxyl group content in the copolymer, and the number of hydroxyl groups in one molecule. There was variation. Therefore, when reacted with a polyfunctional compound having reactivity with a hydroxyl group, an unreacted copolymer remains, there is a large variation in the distance between reaction points, and a play not directly involved in the crosslinked structure after the reaction. A polymer which has sufficient elongation (bendability is good) and is also tough cannot be obtained because of the formation of chain portions and the remaining hydroxyl groups that do not participate in the reaction. On the other hand, polyethers having a hydroxyl group at the end, polyesters, polybutadiene, etc., have a hydroxyl group at the polymer end, so there are few defects such as copolymers of vinyl monomers having a hydroxyl group in the side chain, but polyethers. In the case of, the main chain has an ether bond, in the case of polyester, the main chain has an ester bond, and in the case of polybutadiene, it has an unsaturated double bond in the main chain, which results in weather resistance, water resistance, heat resistance, etc. It has the disadvantage of not being good.

As described above, at present, as a raw material for the above-mentioned applications, various resin additives and polymers having a hydroxyl group, which are used as the raw material thereof, etc., the toughness, elongation (bending workability) and weather resistance are improved. There is no one that satisfies all the required performances such as durability and water resistance. Such a problem is considered to be solved by a vinyl polymer having hydroxyl groups at both ends, but as described below, polar vinyl such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, etc. At present, a method for industrially producing a polymer having a hydroxyl group at both ends from a wide range of vinyl-based monomers including system-based monomers has not been established.

As a method for producing a vinyl polymer having a hydroxyl group at the terminal, for example, 2-mercaptoethanol or the like is used as a chain transfer agent to introduce one hydroxyl group at one terminal of the polymer and 2-hydroxymethacrylic acid is used. There is a method of obtaining a polymer having a hydroxyl group at the terminal by introducing another hydroxyl group on average into the polymer molecule by copolymerization with ethyl or the like.

However, in this method, although an average of two hydroxyl groups is introduced per one molecule of the polymer, only one of the average two hydroxyl groups is introduced into one end of the polymer. One hydroxyl group is introduced not in the terminal but in the middle of the main chain. In addition, since another hydroxyl group is introduced by copolymerization, the total number of hydroxyl groups per molecule of the polymer shows a distribution (variation) such as one or three or more, and also between hydroxyl groups. Wide distribution is possible in the distance. Therefore, the obtained polymer can hardly exhibit the advantages of the polymer having hydroxyl groups at both ends as described above. In addition, the addition of the mercaptan compound causes a problem that the polymerization is extremely slowed and the polymerization rate does not increase, or the odor of the remaining mercaptan remains.

As a method for producing a vinyl-based polymer having hydroxyl groups at both ends, for example, as shown in the following (i) to (iii), the vinyl-based monomer is present in the presence of various initiators and chain transfer agents. There is a method of radically polymerizing the monomer. (I) A method of obtaining a polymer having hydroxyl groups at both ends by polymerizing styrene or butadiene using an initiator having a hydroxyl group (“J. Polym. Sc”).
i. , Part A1 ", Volume 9, pages 2029, 19".
See 71 years).

(Ii) by a method of thermal polymerization or photopolymerization using a dithiocarbamate or thiuram disulfide having a hydroxyl group as an initiator, or by using the above dithiocarbamate or thiuram disulfide as a chain transfer agent and hydrogen peroxide, etc. Is used as an initiator to carry out polymerization to obtain a polymer having hydroxyl groups at both ends (see JP-A-61-271306).

(Iii) A method of obtaining a polymer having hydroxyl groups at both ends by polymerization using a disulfide, trisulfide or the like having hydroxyl groups at both ends as a chain transfer agent (see JP-A-54-47782). .

[0015]

However, the above-mentioned conventional methods for producing a polymer having hydroxyl groups at both ends (i) to
(Iii) has the following drawbacks, and a polymer having hydroxyl groups at both ends can be reliably, inexpensively, and easily and industrially synthesized from many types of vinyl monomers. It's not easy.

First, in the method (i), usable vinyl-based monomers are limited to butadiene and styrene, and polar vinyl-based monomers such as acrylic acid esters and methacrylic acid esters cannot be used. There was a problem. Next, in the method (ii), thiuram disulfide having a functional group such as a hydroxyl group is unstable, and thus it is difficult to handle them. Further, there is a problem that the produced polymer is colored yellow.

Finally, the method (iii) has the same problem as the method (ii), and the initiator segment is inserted at the polymer end, and a polymer having a hydroxyl group only at one end is by-produced. Then, there was a problem that a polymer having a low number of terminal hydroxyl groups was formed. As described above, industrially producing polymers having hydroxyl groups at both ends from a wide range of vinyl-based monomers including polar vinyl-based monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester. The method of doing so is not yet established.

In view of the above circumstances, the present invention provides a wide range of vinyl-based monomers including polar vinyl-based monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester at both ends. An object of the present invention is to provide a method capable of easily and inexpensively obtaining a polymer having a hydroxyl group and efficiently.

[0019]

In order to solve the above-mentioned problems, a method for producing a polymer according to the present invention comprises a step of polymerizing a vinyl monomer (a) in the presence of an alcohol (b),
A method of using an initiator system (c) which essentially requires an organic peroxide, wherein a non-phosphorus inorganic acid (d) is further used and the above four (a), (b) and (c) are used. , (D) are not used substantially.

Here, the polymer obtained by this production method is a polymer having a hydroxyl group at both ends (hereinafter, this polymer may be referred to as "polymer A"). Hereinafter, first, a method for producing a polymer according to the present invention will be described. The vinyl-based monomer (a) used in the present invention is not particularly limited as long as it is a conventionally known vinyl-based monomer. For example, (meth) acrylic acid; methyl (meth) acrylate, (meth) Ethyl acrylate, (meth)
Butyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
(Meth) acrylic acid alkyl esters such as n-octyl acrylate, dodecyl (meth) acrylate and stearyl (meth) acrylate; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; (meth) (Meth) acrylic acid substitution such as 2-hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane Group-containing alkyl esters;
(Meth) acrylic acid derivatives such as methoxyethyl (meth) acrylate and ethylene oxide adducts of (meth) acrylic acid; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, fumaric acid Aromatic vinyl monomers such as styrene, α-methylstyrene, methylstyrene, chlorostyrene, styrene sulfonic acid and its sodium salt; (meth) acrylic acid perfluoromethyl, (meth) Perfluoroethyl acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate,
Perfluorooctyl (meth) acrylate, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2- (meth) acrylate
Perfluoroethyl ethyl, 2- (meth) acrylic acid 2-perfluoromethyl-2-perfluoroethyl methyl,
(Meth) acrylic acid triperfluoromethylmethyl,
2- (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic acid 2-per Fluorine-containing vinyl monomers such as fluorohexadecylethyl, perfluoroethylene, perfluoropropylene and vinylidene fluoride; trialkyloxysilyl group-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Silicon-containing vinyl monomers such as γ- (methacryloyloxypropyl) trimethoxysilane; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenyl Reimido, maleimide derivatives such as cyclohexyl maleimide; acrylonitrile, methacrylonitrile group-containing vinyl monomers such as nitrile;
Amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or in combination of two or more.

As seen above, the vinyl monomer (a) used in the present invention may have a functional group such as a hydroxyl group, a carboxyl group or an amino group in the molecule. Especially when a relatively high crosslinking density is required, it is rather preferable to use a small amount of a vinyl-based monomer having a functional group in combination, for example, for coating applications. The amount of the vinyl-based monomer having a functional group is not particularly limited. For example, in the case of a vinyl-based monomer having a hydroxyl group, the hydroxyl group is added to the total amount of the vinyl-based monomer (a) used. The vinyl-based monomer has preferably 1 to 50% by weight, and more preferably 5 to 30% by weight.

It is preferable that the vinyl monomer having a carboxyl group is 0.5 to 25% by weight.
More preferably, it is 10% by weight. As described above, the vinyl-based monomer (a) is not particularly limited as long as it is a conventionally known vinyl-based monomer. It is preferable that the main component is a (meth) acrylic acid-based monomer. In this case, it is preferable that the (meth) acrylic acid-based monomer is contained in an amount of 40% by weight or more based on the entire vinyl-based monomer (a).

When gloss and hardness of the coating film are required, it is preferable to use an aromatic vinyl monomer.
In this case, it is preferable that the aromatic vinyl-based monomer is contained in an amount of 40% by weight or more based on the entire vinyl-based monomer (a). Further, when water repellency, oil repellency, stain resistance and the like are required, it is preferable to use a fluorine-containing vinyl monomer. In this case, it is preferable that the fluorine-containing vinyl monomer is contained in an amount of 10% by weight or more based on the entire vinyl monomer (a).

When adhesion with an inorganic material and stain resistance are required, it is preferable to use a silicon-containing vinyl monomer. In this case, it is preferable that the silicon-containing vinyl-based monomer is contained in an amount of 10% by weight or more based on the entire vinyl-based monomer (a). In the present invention, the alcohol used as the alcohol (b) may be a monofunctional alcohol having only one hydroxyl group in one molecule, or a polyfunctional alcohol having two or more hydroxyl groups in one molecule. It may be. Further, a monofunctional alcohol and a polyfunctional alcohol may be used in combination. The monofunctional alcohol is not particularly limited, and examples thereof include ethyl alcohol, methyl alcohol, propyl alcohol, butyl alcohol, tertiary butyl alcohol, pentyl alcohol, C _{12 to} C ₁₄ higher alcohols, methoxyethanol, ethoxyethanol, and propylene alcohol. One or more of oxyethanol, ethylene glycol monoacetate, cyclohexanol, benzyl alcohol, phenethyl alcohol and the like can be mentioned. The polyfunctional alcohol is not particularly limited, but for example, ethylene glycol, 1,2-propanediol, 1,3-
Propanediol, 1,2-butanediol, 1,3-
Butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, neopentyl glycol, 1,5-pentanediol, 2 , 3-
Pentanediol, 2,4-pentanediol, 1,6
-Alkylene glycols such as hexanediol; Hydroquinone diethylol ether; Ethylene glycol derivatives such as diethylene glycol and triethylene glycol; Aliphatic polyfunctional alcohols such as sorbitol, cyclohexanediol, xylylenediol; Glycerol and monoacetin, monolaurin, monoolein, mono Glycerol fatty acid esters such as palmitin and monostearin and glycerol monoallyl ether,
Thymyl alcohol, glycerol monomethyl ether,
1 or 2 substituted derivatives of glycerol such as glycerol monoethers such as batyl alcohol; trimethylolpropane and its 1 or 2 substituted derivatives; 1-3 of pentaerythritol such as pentaerythritol and pentaerythritol dioleate, pentaerythritol distearate. Substituted derivative; sorbitan fatty acid ester; erythritol, threose, ribose, arabinose, xylose, lyxose, allose, altose, glucose, mannose, gulose, idose, galactose, talose, fructose, apiose, rhamnose, psicose, sorbose, tagitose, ribulose, xylulose. Saccharides such as monosaccharides and disaccharides such as sucrose, maltose and lactose One or two or more thereof. These alcohols (b) may be appropriately selected depending on the intended use of the polymer A to be obtained. For example,
When the polymer A is used as a raw material for the thermoplastic resin composition or the thermoplastic polymer, it is preferable to use a monofunctional alcohol, and when the polymer A is used as a raw material for the thermosetting resin composition or the thermosetting polymer, The use of polyfunctional alcohols is preferred. Further, among the above alcohols (b), use of ethylene glycol, 1,4-butanediol, trimethylolpropane, glycerol, pentaerythritol and sorbitol is particularly preferable.

The molecular weight of the alcohol (b) is not particularly limited, but is preferably 300 or less. Molecular weight is 300
If it exceeds, the viscosity of the alcohol increases, the solubility of the alcohol in the reaction system decreases, or the viscosity of the reaction system increases, and the average number of terminal hydroxyl groups (Fn (OH)) of the produced polymer is increased.
It is not preferable because the physical properties such as are deteriorated. The alcohols (b) are not limited to those containing only carbon, hydrogen and oxygen as constituent elements. For example, it may contain a nitrogen element or a sulfur element in addition to the above three elements.

The nitrogen element-containing alcohol that can be used is not particularly limited, but examples thereof include amine-based polyfunctional alcohols such as phenyldiethanolamine, triethanolamine, triisopropanolamine, diethanolamine, diisopropanolamine, and trishydroxymethylaminomethane. Tris hydroxycyanuric acid and the like can be mentioned.

As for the alcohol containing elemental sulfur, various bonds containing elemental sulfur, for example, C═S bond and C—S.
-C bond, SO ₂ bond, SO ₃ bond, SH bond or S
An alcohol having an _n- bond (n ≧ 2) or the like can be used. The sulfur element-containing alcohol that can be used is not particularly limited, and examples thereof include mercaptoethanol, methanesulfonylethanol, methylmercaptoethanol, ethylmercaptoethanol, thiodiethylene glycol, 2-hydroxyethyl disulfide, thiodiethylene glycol, ethylene bis-2-hydroxy. Ethyl sulfide, bishydroxyethyl sulfone, N, N-bis (2-hydroxyethyl) taurine and its metal salt, laurylthiopropionic acid thiodiethanolamine salt, ethylene oxide adduct of thioethylene glycol, bis (2-hydroxyethyl) bisphenol- S, bis (2-hydroxyethyl) tetrabromobisphenol-S, bis (2-hydroxyethyl) tetramethylbisphenol-S, Scan (2-hydroxyethyl) diphenyl bisphenol -S, bis (2-hydroxyethyl) thio-diphenol and the like.

The number of terminal functional groups can be easily controlled by appropriately selecting the type of alcohol (b). As a result, without using a vinyl-based monomer having a functional group in combination, the toughness, the weather resistance, and the water resistance, which are the characteristics of the terminal functional polymer, are not impaired, and the crosslinking density with a balanced performance of the crosslinked body is obtained. It becomes possible to obtain. The weight ratio of the alcohols (b) and the vinyl-based monomer (a) used [alcohol (b): vinyl-based monomer (a)] is preferably 1:20 to 20: 1. , And more preferably 1: 1
It is 0 to 10: 1. Further, the alcohols (b) are preferably 2 mole times or more, and more preferably 50 mole times or more, with respect to the initiator system (c).

There are no particular restrictions on the organic peroxide used in the initiator system (c) which essentially requires the organic peroxide used in the present invention, and examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide,
Ketone peroxides such as 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3,5 -Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valate, Peroxyketals such as 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, di-isoprouropylbenzene hydroperoxide, 2- (4-methylcyclohexyl) -Propane hydroperoxa De, 2,5-dimethylhexane -
2,5-dihydroperoxide, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide,
t-butylcumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2 , 5-dimethyl-
Dialkyl peroxides such as 2,5-di (t-butylperoxy) hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5. -Diacyl peroxides such as trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, di-isopropyl peroxydicarbonate, di-2- Ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2- Peroxydicarbonates such as tylhexyl peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate and diallylperoxydicarbonate, t-butylperoxy Acetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxy-2-ethylexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t
-Butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, Peroxyesters such as cumyl peroxy octoate, t-hexyl peroxy pivalate, t-butyl peroxy neohexanoate, t-hexyl peroxy neohexanoate, cumyl peroxy neohexanoate, acetylcyclohexyl Examples thereof include sulfonyl peroxide and t-butyl peroxyallyl carbonate. Cyclohexanone peroxide and benzoyl peroxide are particularly preferable.
The organic peroxide may be used alone or in combination of two or more.

As the initiator system (c) containing an organic peroxide as an essential component used in the present invention, for example, a compound (e) capable of promoting polymerization by being combined with an organic peroxide can be used. There are a case where it is used together with an oxide and a case where it is used alone with an organic peroxide. Compound (e)
Examples thereof include an organic peroxide decomposition catalyst and a reducing compound that undergoes a redox reaction with an organic peroxide. That is, the initiator system (c) that essentially requires an organic peroxide may be an organic peroxide alone, or alternatively, an organic peroxide may be an essential component, and an organic peroxide decomposition catalyst and a reducing agent may be used. It may be a mixture containing one or more compounds selected from the group consisting of compounds and capable of promoting polymerization.

The compound (e) capable of promoting the polymerization by combining it with an organic peroxide will be specifically described below. The organic peroxide decomposition catalyst that is an example of the compound (e) is not particularly limited, but examples thereof include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, sulfuric acid. , Metallic salts of inorganic acids such as nitric acid, perchloric acid and hydrobromic acid; carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolacic acid and benzoic acid and their metal salts and esters; pyridine, indole and its Examples thereof include heterocyclic amines such as derivatives, imidazole and its derivatives, and carbazole and its derivatives. These may use only 1 type and may use 2 or more types together.

The reducing compound which is an example of the compound (e) and which carries out a redox reaction with an organic peroxide is not particularly limited, but for example, an organometallic compound such as ferrocene; iron naphthenate, copper naphthenate, Inorganic metal compounds that can generate metal ions such as iron, copper, nickel, cobalt, and manganese exemplified by nickel naphthenate, cobalt naphthenate, and manganese naphthenate, boron trifluoride ether adduct, potassium permanganate. Inorganic compounds such as; sulfur dioxide, sulfites, sulfuric acid mono- or di-alkyl esters, sulfuric acid mono- or di-allyl esters, bisulfites, thiosulfates, sulfoxylates, benzenesulfinic acid and the like. Substituted compounds, sulfur-containing compounds such as homologues of cyclic sulfinic acid such as paratoluenesulfinic acid; Chill mercaptan, decyl mercaptan, dodecyl mercaptan, mercaptoethanol, alpha-mercaptopropionic acid, thioglycolic acid,
Mercapto compounds such as thiopropionic acid, α-thiopropionic acid sodium sulfopropyl ester and α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine and hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde Aldehydes such as n-butyraldehyde, isobutyraldehyde and isovalerianaldehyde; and ascorbic acid. These may use only 1 type and may use 2 or more types together.

The initiator system (c) is not limited to those mentioned above. For example, an organic peroxide, or an organic peroxide and the above compound (e) are combined with a conventionally known radical initiator such as an azo initiator such as AIBN (azobisisobutyronitrile) or hydrogen peroxide. It can also be used in combination with one or more of the agents. The amount of the initiator system (c) used is
Although it is naturally determined by the molecular weight of the target polymer A,
Generally, it is 0.1 to 2 with respect to the vinyl-based monomer (a).
It is preferably 0% by weight.

The non-phosphorus inorganic acid (d) used in the present invention is not particularly limited, but examples thereof include hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, perchloric acid, and chlorous acid. Acids, hypochlorous acid, periodic acid, sulfuric acid, fuming sulfuric acid, sulfurous acid, nitric acid, fuming nitric acid, manganic acid, permanganic acid, chromic acid, dichromic acid, and various other non-phosphorus solid acids, and the like. Of these, sulfuric acid and hydrochloric acid are preferable. The non-phosphorus inorganic acid (d) may be used alone or in combination of two or more.

The preferred amount of the non-phosphorus inorganic acid (d) used is 0.05 to 10% by weight based on the total amount of the components. In the production method of the present invention, components other than the vinyl-based monomer (a), the alcohols (b), the initiator system (c) that essentially requires an organic peroxide, and the non-phosphorus inorganic acid (d) are substantially contained. Not to use it.

Specifically, the components other than the vinyl monomer (a), the alcohols (b), the initiator system (c) which essentially requires an organic peroxide, and the non-phosphorus inorganic acid (d) are used. , So that the total amount of the components is about 10% by weight or less. And, the components other than (a), (b), (c) and (d) are preferably 5% by weight or less, and most preferably
This means that no components other than (a), (b), (c) and (d) are used.

However, the above four persons (a), (b),
Surfactant (x) as a component other than (c) and (d),
Use within a range of less than 10% by weight based on the total amount of the components may improve the introduction of hydroxyl groups into the polymer A to be obtained but does not decrease it, and therefore, it does not pose any problem.
The surfactant (x) is not particularly limited, but examples thereof include triethylbenzylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, and N chloride. -Laurylpyridinium, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, trimethylphenylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide,
Tetra-n-butylammonium hydrogensulfate, N-benzylpicolinium chloride, tetramethylammonium iodide, tetra-n-butylammonium iodide, N-lauryl-4-picolinium chloride, N-lauryl-4-picolinium chloride Such as quaternary ammonium salt; phosphonium salt such as tetrabutylphosphonium chloride; sulfonium salt such as trimethylsulfonium iodide; onium salt such as; or polyoxyethylene-polypropylene oxide block copolymer; polyoxyethylene sulfate ester, etc. Polyoxyethylene-based surfactants; higher alcohols such as lauryl alcohol and stearyl alcohol; and sulfuric acid esters of these higher alcohols and metal salts of the sulfuric acid esters; lauric acid, sulfur Higher fatty acid and metal salts and sorbitan esters of higher fatty acids such as stearic acid. These may use only 1 type,
You may use together multiple types.

When the surfactant (x) is used, its amount is less than 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of components. When the surfactant (x) is used in an amount of 10% by weight or more based on the total amount of components, the surfactant (x)
It is not preferable because the average number of terminal hydroxyl groups (Fn (OH)) of the obtained polymer is decreased by a side reaction such as a chain transfer reaction.

Among the above-mentioned surfactants (x), a surfactant having hydroxyl groups at both ends itself like a polyoxyethylene-polypropylene oxide block copolymer is incorporated into a crosslinked structure. Since the adverse effects on the toughness, weather resistance and water resistance of the crosslinked product do not appear, purification and removal are not required, which is preferable. The polymerization vessel (reactor for carrying out the polymerization reaction) used in the present invention may be a batch type such as a general tank type reactor or a kneader, and a piston flow tube type type or a polymer type Depending on the viscosity, a continuous type extruder such as a twin-screw extruder or a continuous kneader may be used. Also, it can be used in a semi-batch type reactor without any problem, but the concentration ratio of each additive in the reactor can be easily controlled by adding each additive in the middle of the tube, and that the residence time is constant From the viewpoint of good productivity and the like, it is preferable to use a tubular reactor, an extruder or a continuous kneader. Regarding the proper use of tubular reactor, extruder and continuous kneader, use a tubular reactor when the reaction mixture after polymerization has a low viscosity, and an extruder or continuous kneader when it has a relatively high viscosity. Is preferred.

However, a suitable material should be selected for the liquid contact part of these devices, and in general, SUS31
6, 304L, Teflon, aluminum, glass, etc. can be mentioned. Among these, Teflon, aluminum and glass are preferable, and Teflon and glass are most preferable. The structure of the tubular reactor is not particularly limited, and a conventionally known tubular reaction such as a single-tube type, a multi-tube type, or a mixer having no moving parts (such as Noritake Company or Sumitomo Sulzer) You can use it if it is a container,
From the viewpoints of mixing and heat exchange efficiency, it is preferable to use a tubular reactor using a mixer having no moving parts. Similarly, for extruders and continuous kneaders, uniaxial type,
Although a conventionally known extruder such as a twin-screw type can be used, it is preferable to use a twin-screw type extruder or a continuous kneader in terms of mixing and heat exchange efficiency.

In the present invention, the reaction can be carried out at atmospheric pressure, but it can also be carried out under pressure in an autoclave or an extruder. The polymerization temperature in the production method of the present invention is also not particularly limited, and there is no problem as long as it is from room temperature to 200 ° C at which ordinary radical polymerization is carried out. The production method of the present invention may require a step of removing excess alcohols (b) after completion of the polymerization. Alcohols used at that time (b)
When the produced polymer A is compatible with the produced polymer A, the alcohols (b) can be removed by devolatization under reduced pressure using a kettle or a twin-screw extruder. When the alcohols (b) and the polymer A are incompatible with each other, the reaction mixture after completion of the polymerization is allowed to stand or separate, or the polymer A is added to the reaction mixture.
Is dissolved, but alcohols (b) is not dissolved. A solvent is added to reduce the viscosity of the polymer layer, and the polymer layer is then separated by standing to remove most of the alcohols (b), followed by liquid-liquid extraction. Alternatively, the remaining alcohols (b) can be removed by vacuum devolatilization.

The molecular weight of the polymer A produced according to the present invention is not particularly limited, but the number average molecular weight is in the range of 500 to 100,000 in order to exert the characteristics resulting from having a reactive hydroxyl group at the terminal. Is preferable, and the number average molecular weight is more preferably 1,000 to 50,000. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer A produced by this invention is 1.8 times or more of the number of hydroxyl groups (number of hydroxyl groups per alcohol molecule) of the used alcohols (b). If so, it is very preferable because it can exhibit the physical properties almost equivalent to those of the ideal one (twice). If it is 1.5 times or more,
It can exhibit physical properties that are quite close to ideal. For example, when the alcohol (b) is a bifunctional alcohol such as ethylene glycol (the number of hydroxyl groups per molecule of alcohol is 2), the Fn (OH) of the polymer A is ideally 4.0. However, if it is 3.6 to 4.0, it is possible to exhibit the same physical properties as the ideal one, which is very preferable. If it is at least 3.0, physical properties close to ideal can be exhibited. When the alcohol (b) is a monofunctional alcohol such as ethylene glycol monoacetic acid ester (the number of hydroxyl groups per alcohol molecule is 1), the Fn (OH) of the polymer A is ideally 2. 0,
It is very preferably 1.8 to 2.0, and preferably at least 1.5.

The polymer A obtained by the production method of the present invention has a terminal hydroxyl group which can be easily polymerized with a polymerizable unsaturated group such as an amino group, a carboxyl group or a vinyl group by utilizing a conventionally known organic reaction. , Epoxy group, silanol group, alkoxysilyl group, hydrosilyl group, mercapto group, oxazoline group, lactone group, azlactone group, ethynyl group, maleimide group, formyl group, bromine, chlorine, etc. it can.

Next, the polymer A produced by the present invention
The composition in which is essential will be described. This composition
Polymer A and functional groups capable of reacting with hydroxyl groups are 2 per molecule
The compound (f) having one or more units is included as an essential component. Polymer A may use only 1 type and may use 2 or more types together. The weight ratio of the polymer A and the compound (f) (polymer A / compound (f)) contained in this composition is not particularly limited, but is 99.99 / 0.
It is preferably 01 to 40/60, and 99.9 /
It is more preferably 0.1 to 60/40.

This composition comprises, in addition to the polymer A, a conventionally known low molecular weight compound having a hydroxyl group and a conventionally known polymer having a hydroxyl group (polymer polyol, acrylic polyol, polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene). (Polyol, polyolefin polyol, etc.).

The compound (f) having two or more functional groups capable of reacting with the hydroxyl group in one molecule is not particularly limited, but for example, a compound (g) having two or more isocyanate groups in one molecule (g). ), An aminoplast resin (h) such as a methylolated melamine and an alkyl ether compound or a low condensation product thereof, a compound (i) having two or more carboxyl groups in one molecule such as a polyfunctional carboxylic acid and a halide thereof. Is mentioned.

The compound (g) having two or more isocyanate groups in one molecule is a so-called polyfunctional isocyanate compound. As the polyfunctional isocyanate compound (g), any conventionally known compound can be used, and for example, tolylene diisocyanate (“TD
I "), 4,4'-diphenylmethane diisocyanate (also referred to as" MDI "), hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Isocyanate compounds such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate; Burette polyisocyanate compounds such as Sumidule N (Sumitomo Bayer Urethane Co.); Desmodur IL, HL (Bayer AG) , Coronate EH (Japan Polyurethane Industry Co., Ltd.)
Polyisocyanate compounds having an isocyanurate ring such as SUMIJURE L (manufactured by Sumitomo Bayer Urethane Co., Ltd.) and adduct polyisocyanate compounds such as Coronate HL (manufactured by Nippon Polyurethane Co.). be able to. These may be used alone or in combination of two or more. In addition, blocked isocyanate may be used.

In order to take advantage of the excellent weather resistance of the composition containing the polymer A and the polyfunctional isocyanate compound (g), examples of the polyfunctional isocyanate compound (g) include hexamethylene diisocyanate and hydrogen. Diphenylmethane diisocyanate, Sumidule N
It is preferable to use an isocyanate compound having no aromatic ring such as (Sumitomo Bayer Urethane Co., Ltd.).

The mixing ratio of the polymer A and the polyfunctional isocyanate compound (g) is not particularly limited,
For example, the ratio (NCO / OH (molar ratio)) of the isocyanate group of the compound (g) to the hydroxyl group of the polymer A is preferably 0.5 to 1.5,
It is more preferably 8 to 1.2. However, when this composition is used in applications where excellent weather resistance is required, it may be used in a molar ratio up to about NCO / OH = 3.0.

The polymer A which is a component in this composition
In order to accelerate the urethanization reaction between the polyfunctional isocyanate compound (g) and the polyfunctional isocyanate compound (g), a known catalyst such as an organic tin compound or a tertiary amine may be used as needed. Although the aminoplast resin (h) is not particularly limited, for example, a reaction product of a triazine ring-containing compound represented by the following general formula 1 and formaldehyde (methylol compound), a compound of the triazine ring-containing compound and formaldehyde Examples include low-condensation products, derivatives thereof, urea resins, reaction products of urea resins and formaldehyde (methylol compounds), low-condensation products of urea resins and formaldehyde, derivatives thereof, and the like.

[0051]

[Chemical 1]

The triazine ring-containing compound represented by the general formula 1 is not particularly limited, but examples thereof include melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, vinylguanamine and the like. These may be used alone,
You may use 2 or more types together. The reaction product of the triazine ring-containing compound and formaldehyde or a derivative thereof is not particularly limited, but examples thereof include hexamethoxymethylmelamine and tetramethoxymethylbenzoguanamine. As the low-condensation compound or a derivative of said triazine ring-containing compound and formaldehyde is not particularly limited, for example, the triazine ring-containing _{compound, -NH-CH 2 -O-CH} 2 -NH-
Binding and / or low condensate products and alkyl-etherified formaldehyde resin was several bonded via -NH-CH ₂ -NH- bond [Cymel (manufactured by Mitsui Cyanamid Co.
Manufactured)] and the like. These aminoplast resins (h) may be used alone or in combination of two or more.

Aminoplast resin (h), examples of which were given above
The ratio of the triazine ring-containing compound and formaldehyde used in synthesizing the compound varies depending on the application used, but the molar ratio of the triazine ring-containing compound and formaldehyde (triazine ring-containing compound / formaldehyde) is 1 to It is preferably in the range of 6,
The range of 1.5 to 6 is more preferable.

The ratio (weight ratio) of the polymer A to the aminoplast resin (h) in the composition containing the polymer A and the aminoplast resin (h) as the compound (f) as an essential component was 95: 5:50:50 is preferable, 80: 2
0 to 60:40 is more preferable. In the composition containing the polymer A and the aminoplast resin (h) as essential components, it is free to use a conventionally known catalyst such as paratoluenesulfonic acid or benzenesulfonic acid for promoting the reaction.

The compound (i) having two or more carboxyl groups in one molecule is not particularly limited, but for example, oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, phthalic acid, phthalic anhydride, terephthalic acid,
Trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, diphenic acid, polyfunctional carboxylic acid such as naphthalenedicarboxylic acid or its anhydride,
In addition, these halides, polymers having a plurality of carboxyl groups and the like can be mentioned. Compound (i) is
You may use only 1 type and may use 2 or more types together.
The molar ratio of the compound (i) to the hydroxyl group in the polymer A (compound (i) / hydroxyl group in the polymer A) is preferably 1 to 3, more preferably 1 to 2.

A composition containing as an essential component a polymer A and a compound (f) having two or more functional groups capable of reacting with a hydroxyl group in one molecule (hereinafter, this composition is simply referred to as "composition A").
Sometimes called. When a) is used as a coating composition, the hardness of the coating film is required, and therefore a certain degree of crosslink density is required. Therefore, as the polymer A used for coating purposes, those having a hydroxyl value of about 20 to 450 are preferable. That is, when the monomer having a hydroxyl group is not copolymerized, the number average molecular weight of the polymer A is 500 to 1
About 2000 is preferable. However, the number average molecular weight is 12
Those having a molecular weight of more than 000 can be used by copolymerizing a monomer having a hydroxyl group. When the composition A is used as a coating composition, the Tg (glass transition temperature) of the polymer A is preferably -30 ° C to 100 ° C,
-10 ° C to 60 ° C is more preferable. By adjusting the type and proportion of the vinyl-based monomer (a) used, the desired T
Polymer A having g can be synthesized. When the aminoplast resin (h) is used as the compound (f), it is preferable to copolymerize an acid group-containing vinyl monomer as the internal acid catalyst.

When the composition A is used as a coating composition, in addition to the polymer A, a conventionally known low molecular weight compound having a hydroxyl group and a conventionally known polymer having a hydroxyl group (polymer polyol, acrylic polyol, polyether polyol, (Polyester polyol, polycarbonate polyol, polybutadiene polyol, polyolefin polyol, etc.), a conventionally known coating resin, etc. may be contained.

When the composition A is used as a pressure-sensitive adhesive composition, the Tg of the polymer A is preferably −20 ° C. or lower, and its molecular weight (weight average molecular weight) is 100.
It is preferably from 0 to 1,000,000. When a low molecular weight polymer A having a weight average molecular weight of about 1,000 to 10,000 is applied to a substrate by combination with a bifunctional isocyanate compound or the like and then chain-extended and used as an adhesive, a vinyl having a functional group is used. The viscosity of the pressure-sensitive adhesive composition is low as compared with the case of using a conventional polymer obtained by copolymerizing a system monomer (usually, one having a weight average molecular weight of 100,000 or more is used), and therefore, The effect that the conventional pressure-sensitive adhesive composition does not have can be obtained such that the amount of the solvent used is reduced and the workability is improved. Further, in order to further improve the adhesiveness with the base material, it is preferable to copolymerize the acid group-containing monomer.

When the composition A is used as a pressure-sensitive adhesive composition, the composition may contain, if necessary, conventionally known additives such as a tackifier, a plasticizer, a filler and an antiaging agent. May be included. The tackifier that can be used is not particularly limited, and examples thereof include rosin-based, rosin ester-based, polyterpene resin, chroman-indene resin, petroleum-based resin, and terpene phenol resin. The plasticizer is not particularly limited, but examples thereof include liquid polybutene, mineral oil, lanolin, liquid polyisoprene, and liquid polyacrylate. The filler is not particularly limited, and examples thereof include zinc white, titanium white, calcium carbonate, clay and various pigments. The anti-aging agent is not particularly limited, but examples thereof include rubber-based antioxidants (phenol-based and amine-based) and metal dithiocarbamates. Each of the tackifiers, plasticizers, fillers and antioxidants listed above may be used alone or in combination of two or more.

When the composition A is used as an adhesive composition, the polymer A has a molecular weight (weight average molecular weight) of 1,000.
It is preferably ˜1,000,000. This polymer A
Can be used as a one-component or two-component adhesive by combining with a conventionally known isocyanate compound or the like. When the composition A is used as a composition for adhesives, in the composition, if necessary, a conventionally known composition,
Additives such as polyols (low molecular weight polyols and high molecular weight polyols), tackifiers, coupling agents, thixotropic agents, inorganic fillers and stabilizers may be included. The polyols that can be used are not particularly limited, and examples thereof include low molecular weight polyols such as ethylene glycol (also referred to as EG) and diethylene glycol (D
EG), dipropylene glycol (also called DPG), 1,4-butanediol (also called 1,4-BD), 1,6-hexanediol (also called 1,6-HD), neopentyl glycol ( NPG), trimethylolpropane (also referred to as TMP), and the like, and polyether polyol [polyethylene glycol (also referred to as PEG), polypropylene glycol (also referred to as PPG), ethylene oxide / propylene oxide copolymer as a high molecular weight polyol. (Also referred to as EO / PO copolymer), polytetramethylene glycol (P
Also referred to as TMEG)], polyester polyol, castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, polymer polyol, polyolefin polyol, acrylic polyol and the like. The tackifier is not particularly limited, and examples thereof include a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, and a xylene resin. The coupling agent is not particularly limited,
Examples thereof include silane coupling agents and titanium coupling agents. The inorganic filler is not particularly limited,
For example, carbon black, titanium white, calcium carbonate, clay and the like can be mentioned. The thixotropic agent is not particularly limited, and examples thereof include Aerosil and Disparlon. The stabilizer is not particularly limited, for example, an ultraviolet absorber, an antioxidant, a heat stabilizer,
A hydrolysis-resistant stabilizer etc. can be mentioned. The above-mentioned polyols, tackifiers, coupling agents,
The thixotropic agent, inorganic filler and stabilizer are each 1
Only one species may be used, or two or more species may be used in combination.

The application of the above-mentioned adhesive is not particularly limited, but for example, adhesives for food packaging, adhesives for shoes / footwear, adhesives for decorative paper, adhesives for wood, structural (automobiles,
Examples include septic tanks, housing) adhesives, magnetic tape binders, fiber processing binders, fiber treatment agents, and the like. Composition A
When using as a urethane foam composition, in the composition, if necessary, conventionally known polyols (other than the polymer A obtained by the production method of the present invention,
Low molecular weight polyols, high molecular weight polyols, etc.), polyisocyanate (eg TDI, MDI etc.), catalyst (eg amine type, tin type etc.), water, surfactant (eg silicon type, non-ionic type, Ionic, etc.), additives (eg, flame retardants, antimicrobial agents, colorants, fillers, stabilizers, etc.), foaming aids (eg, halogenated hydrocarbons, etc.)
Etc. may be included.

When the composition A is used as a sealant composition, the polymer A has a molecular weight (weight average molecular weight) of 10
It is preferably from 0 to 1,000,000. Composition A
When used as a sealant composition, in the composition, if necessary, conventionally known polyols (high molecular weight polyols other than the polymer A, etc.), polyisocyanates (eg, TDI, MDI, etc.) , Catalysts (eg amine-based, tin-based, lead-based etc.), inorganic fillers (eg calcium carbonate, talc, clay, silica, carbon black, titanium white etc.), plasticizers [eg dioctyl phthalate (also DOP) , Di-i-decyl phthalate (also called DIDP), dioctyl adipate (DOA)
Etc.)], an anti-drip agent (for example, colloidal silica, hydrogenated castor oil, organic bentonite, surface-treated calcium carbonate, etc.), an antiaging agent (for example, hindered phenols, benzotriazole, hindered amines, etc.) , A foaming inhibitor (eg, dehydrating agent, carbon dioxide absorbent, etc.) may be included.

When a polymer obtained by converting the hydroxyl group of the polymer A obtained by the production method of the present invention into a hydroxysilyl group, an alkoxysilyl group or a mercapto group is used as an essential component of the sealant composition, The sealing material composition becomes a sealing material composition having a crosslinking system different from urethane. Next, the polymer (A) produced by the production method according to the present invention has a compound (j A polymer having a polymerizable unsaturated group at both ends (hereinafter,
This polymer may be referred to as "polymer B").

When synthesizing the polymer B, a compound having two kinds of reactive groups, which are a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, to be reacted with the polymer A in one molecule ( Examples of j) include, but are not limited to, vinyl monomers having an isocyanate group, a carboxyl group, a methylolated triazine ring, or the like. More specifically, for example, methacryloyloxyethyl isocyanate, methacryloyl isocyanate,
Examples thereof include isopropenyl dimethyl benzyl isocyanate, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, halides of these carboxyl groups, and vinylguanamine methylol compounds.

In this reaction, it is free to use a solvent or a conventionally known catalyst. An example of this catalyst is
When the functional group of the compound (j) is an isocyanate group, tertiary amines such as triethylamine, tin compounds such as dibutyltin dilaurate, and the like, the functional group is a carboxyl group or an acid anhydride group. Include amine compounds such as triethylamine and pyridine,
Inorganic acids such as sulfuric acid, and organic acid alkali metal salts such as sodium acetate, when the functional group is a methylolated triazine ring, sulfonic acids such as dodecylbenzene sulfonic acid and other weak acids, etc. Can be mentioned.

When the polymer B is used as an essential component of the composition, other components contained in this composition include, for example, a vinyl monomer having one polymerizable unsaturated group in one molecule. Can be mentioned. The vinyl-based monomer is not particularly limited, and conventionally known ones can be used without any problem. For example, the vinyl-based monomer (a) used when producing the polymer A having hydroxyl groups at both ends is
All of them can be used, and styrene, acrylic acid ester, methacrylic acid ester and the like are particularly preferable. A conventionally known polymerization initiator may be contained in the above composition, if necessary. The energy source for initiating the polymerization is not particularly limited, but for example, light, E
B, radiation, heat, etc. can be used.

Examples of the composition containing the polymer B and the above-mentioned vinyl monomer having one polymerizable unsaturated group in one molecule as essential components include a gel coat resin composition described in detail below, Examples thereof include a resin composition for artificial marble. The gel coat resin composition may optionally contain a polyfunctional vinyl-based monomer having two or more polymerizable unsaturated groups in one molecule. The polyfunctional vinyl-based monomer is not particularly limited, but for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, propylene glycol di (meth) acrylate, methylene. Bisacrylamide, 1,
6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate and the like.
These can be used alone or in combination of two or more.

The weight ratio of the polymer B and the vinyl monomer contained in the gel coat resin composition (polymer B / vinyl monomer) is not particularly limited, but is 10/90 to 60.
/ 40 is preferable, and 20/80 to 50/50 is more preferable. When this ratio is smaller than 10/90, the reaction shrinkage of the gel coat resin layer is too large, so that the shrinkage strain becomes large and it becomes difficult to obtain a good coat surface. Further, when the ratio is more than 60/40, the viscosity of the gel coat resin composition becomes too high, and the workability is likely to be extremely lowered.

To obtain the surface hardness of the gel coat layer,
The Tg of the polymer B and the Tg of the vinyl-based monomer used for this purpose are both preferably 20 ° C. or higher. Further, when it is necessary to increase the crosslink density in order to obtain the surface hardness, a vinyl-based monomer having a hydroxyl group is copolymerized with the polymer A, which is a precursor of the polymer B, or the above polyfunctional compound is used. It is preferable to use the vinyl-based monomer in a proportion of 50% by weight or less.

If necessary, a polymerization inhibitor such as hydroquinone, catechol, or 2,6-ditertiarybutylparacresol is added to the gel coat resin composition. Usually, a commonly used radical polymerization initiator, In particular, it is cured with an organic peroxide initiator or the like. When an organic peroxide initiator is used, various reducing metal salts such as cobalt naphthenate, nickel naphthenate and iron naphthenate, and curing accelerators such as reducing compounds such as amines and mercaptans are used together. You may.

If necessary, the gel coat resin composition may further include a dye, a plasticizer, an ultraviolet absorber and the like, as well as conventionally known thixotropic agents such as silica, asbestos powder, hydrogenated castor oil and fatty acid amide. Various additives such as a filler, a stabilizer, a defoaming agent, and a leveling agent can be added. The artificial marble resin composition may contain, if necessary, a polyfunctional vinyl-based monomer having two or more polymerizable unsaturated groups in one molecule, a filler, a curing agent, a thermoplastic polymer, or the like. Addition of additives etc. is free.

The polyfunctional vinyl-based monomer added to the resin composition for artificial marble according to need is not particularly limited, but for example, the polyfunctional vinyl may be contained in the gel coat resin composition described above. All the system monomers can be used. The addition amount of the polyfunctional vinyl-based monomer is not particularly limited, but the total amount of the polymer B, the vinyl-based monomer having one polymerizable unsaturated group in one molecule, and the polyfunctional vinyl-based monomer. Is preferably 40% by weight or less. This is because if the amount of the polyfunctional vinyl monomer added exceeds 40% by weight, the resulting artificial marble becomes hard and brittle, which is not desirable.

Fillers added as necessary to the resin composition for artificial marble include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, talc, clay, silica, quartz, alumina, zirconia,
Glass powder, glass fiber, marble, limestone, pyroxene,
Examples include natural crushed stones such as amphibole, sandstone, granite, and basalt, and crushed products of unsaturated polyester resin, synthetic resin such as thermosetting acrylic resin and melamine resin. The addition amount of the filler is not particularly limited, but is 100 to 100 with respect to the total amount of the polymer B, the vinyl-based monomer having one polymerizable unsaturated group in one molecule, and the polyfunctional vinyl-based monomer. 80
0% by weight is preferred. If the amount added is less than 100% by weight, the heat resistance and flame retardancy may be insufficient, and if it exceeds 800% by weight, polymer B contains a polymerizable unsaturated group in one molecule. The dispersibility of the filler in the vinyl-based monomer and the polyfunctional vinyl-based monomer having one becomes insufficient, or the fluidity during molding and curing is impaired, and uniform artificial marble cannot be obtained. Sometimes.

The hardener added to the resin composition for artificial marble according to need is not particularly limited, but examples thereof include benzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, and bis (4-t-butylcyclohexyl). ) Peroxydicarbonate, t-butyl peroxybenzoate, t-butyl peroxy octoate and the like can be mentioned. Among them, t-butyl peroxyoctoate and benzoyl peroxide, which are a medium / high temperature curing agent, which give a cured product having good transparency without cracks, are preferable for press molding. The medium / low temperature curing agent may be used alone or in combination with a curing accelerator together with an organic amine or a salt of a polyvalent metal.
t-butylcyclohexyl) peroxydicarbonate (Percadox PX-16, manufactured by Nippon Kayaku Co., Ltd.).

The thermoplastic polymer added as necessary to the artificial marble resin composition is not particularly limited, but examples thereof include (meth) acrylic polymers such as polymethylmethacrylate, and (meth) acrylate-styrene. Copolymer, polystyrene, polyvinyl acetate, styrene-vinyl acetate copolymer, polyvinyl chloride, polybutadiene,
Conventionally known low-shrinkage polymers such as polyethylene, polycaprolactam and saturated polyester may be used alone or in combination. However, if a large amount of thermoplastic polymer for low shrinkage is blended, the viscosity during kneading will increase, making it difficult to obtain a casting compound with a high filler content, and in terms of product transparency and heat resistance. Sometimes you can only get inferior ones. Therefore, the thermoplastic polymer for low shrinkage may be used in a small amount as much as possible and is not particularly limited. However, the polymer B, a vinyl-based monomer having one polymerizable unsaturated group in one molecule and a polyfunctional monomer are used. It is preferably used within a range of 100% by weight or less based on the total amount of vinyl monomers.

Next, the polymer A obtained by the production method of the present invention has a compound (k) and / Or obtained by reacting with an acid anhydride,
The polymer C having a carboxyl group at both ends will be described. When synthesizing this polymer C, the compound (k) having two reactive groups, a functional group capable of reacting with a hydroxyl group and a carboxyl group, which is reacted with the polymer A having a hydroxyl group, is included in one molecule. , But not particularly limited, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid. Examples thereof include acids, dibasic acids such as itaconic acid, and halogen-substituted carboxylic acids such as chloroacetic acid and bromoacetic acid. As described above, the two reactive groups of the functional group capable of reacting with a hydroxyl group and the carboxyl group, which the compound (k) has, may be two carboxyl groups, or other than a carboxyl group such as a halogen group. It may be a combination of a functional group and a carboxyl group. An acid anhydride may be used instead of the compound (k), or the compound (k) and the acid anhydride may be used in combination. The acid anhydride is not particularly limited, and examples thereof include succinic anhydride, glutaric anhydride, phthalic anhydride, maleic anhydride, and itaconic anhydride.

In the reaction of the polymer A having hydroxyl groups at both ends with the compound (k) and / or acid anhydride, it is free to use a solvent or a conventionally known catalyst. Examples of this catalyst include inorganic acids such as sulfuric acid and hydrochloric acid, inorganic bases such as sodium hydroxide and potassium hydroxide when the functional group capable of reacting with the hydroxyl group contained in the compound (k) is a carboxyl group. Examples thereof include tertiary amine compounds such as triethylamine and pyridine, organic acid salts such as sodium acetate and potassium acetate, and in the case of a halogen group, tertiary amine compounds such as pyridine and triethylamine.

The reaction temperature for reacting the polymer A with an acid anhydride is not particularly limited, but is preferably 60 to 100 ° C. When the temperature is lower than 60 ° C, the reaction rate is slow and the final conversion rate is low. Further, when the temperature exceeds 100 ° C., the reaction rate of the dibasic acid increases, but the amount of diester produced increases, which causes a problem that the molecular weight after the reaction increases. Next, a resin composition comprising a polymer C having a carboxyl group at both ends and a compound (1) having two or more functional groups capable of reacting with the carboxyl group in one molecule as essential components. Will be described.

As the polymer C, only one kind may be used,
You may use 2 or more types together. In addition, the weight ratio of the polymer C and the compound (l) contained in the resin composition (polymer C
/ Compound (l)) is not particularly limited, but is 99.9.
It is preferably 9 / 0.01 to 40/60, and 9
More preferably, it is 9.9 / 0.1-60 / 40.

The compound (l) having two or more functional groups capable of reacting with a carboxyl group in one molecule is not particularly limited, but for example, a compound having two or more epoxy groups in one molecule, Compound having two or more hydroxyl groups in molecule, compound having two or more amino groups in one molecule, compound having two or more mercapto groups in one molecule, two or more halogen groups in one molecule A compound having
A compound having two or more oxazoline groups in one molecule,
A compound having two or more aziridine groups in one molecule, 1
Examples thereof include compounds having two or more ester groups in a molecule, compounds having two or more carboxyl groups in a molecule, and the like.

The polymer C may be used as an essential component of the epoxy resin composition. The epoxy resin which is another essential component contained in such an epoxy resin composition is not particularly limited as long as it is a conventionally known epoxy resin, and for example, bisphenol A, bisphenol F, phenol novolac, cresol novolac, Examples include glycidyl ethers of phenols such as brominated bisphenol A; glycidyl ethers of alcohols such as butanol, butanediol, polyethylene glycol, polypropylene glycol; glycidyl esters of acids such as hexahydrophthalic acid and dimer acid. . These may be used alone or in combination of two or more.

If desired, additives such as fillers, pigments and curing agents may be added to the epoxy resin composition. As the filler, aluminum hydroxide,
Magnesium hydroxide, calcium hydroxide, calcium carbonate, talc, clay, silica, kaolin, titanium oxide,
Quartz, quartz glass, alumina, zirconia, glass powder, glass fiber, marble, limestone, pyroxene, amphibole, sandstone, granite, natural crushed stone such as basalt, unsaturated polyester resin, thermosetting acrylic resin and melamine resin, etc. Examples include crushed synthetic resins. Examples of the curing agent include linear aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine; various polyamides having different amine values; mensendiamine, isophoronediamine, bis (4- Alicyclic amines such as aminocyclohexyl) methane; m-xylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,
Aromatic amines such as m-phenylenediamine; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, dodecylsuccinic anhydride, pyropyrohydrate Acid anhydrides such as mellitic acid, methylcyclohexene tetracarboxylic anhydride, trimellitic anhydride, polyazelainic anhydride; phenolic hydroxyl group-containing compounds such as phenol novolac and cresol novolac; polymercaptans; 2,
4,6-tris (dimethylaminomethyl) phenol,
Anionic polymerization catalysts such as 2-ethyl-4-methylimidazole; Cationic polymerization catalysts such as BF ₃ monoethylamine complex; Dicyandiamide, amine adduct, hydrazide, amidoamine, blocked isocyanate, carbamate, ketimine, aromatic diazonium salt, etc. Examples of the latent curing agent include those listed above, and one or more of them can be used.

Next, a polyol component (m) containing the polymer A obtained by the production method of the present invention as an essential component
Will be described with reference to a polyurethane obtained by reacting with a polyfunctional isocyanate compound (g) having two or more isocyanate groups in one molecule. The polyfunctional isocyanate compound (g) having two or more isocyanate groups in one molecule used when synthesizing this polyurethane is
As described above. As the polyol component (m) containing the polymer A as an essential component, the polymer A alone (including the case where two or more kinds of the polymer A are used) may be used, but the polymer A is used in combination with another polyol. You can also Other polyols are not particularly limited, but include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, trimethylolpropane. Partial esterification products of low molecular weight polyols such as pentaerythritol and sorbitol and low molecular weight polyols such as sorbitan fatty acid esters, polyether polyols such as polyethylene glycol, polypropylene glycol, polypropylene glycol-polyethylene glycol block copolymers, and the aforementioned low molecular weight polyols And phthalic acid, phthalic anhydride, terephthalic acid, maleic acid,
Polyester polyol synthesized from polyfunctional carboxylic acid such as maleic anhydride, fumaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, polycarbonate polyol, butadiene and diene-based polyol consisting of butadiene / acrylonitrile copolymer main chain, polyolefin One or more selected from polymer polyols such as polyols, acrylic polyols and polymer polyols can be mentioned.

In this synthesis, the total amount of the polyol component (m) and the polyfunctional isocyanate compound (g) may be reacted in one step, or the polyol component (m) may be reacted in the first step. ) And a polyfunctional isocyanate compound (g) are reacted with each other to first synthesize a polymer (oligomer) having at least one isocyanate group at a terminal, and then the polymer (oligomer) is added in the next step. May be used in combination with another polymer having one hydroxyl group (oligomer) to synthesize polyurethane. However, in the case of the two-step reaction, it may be necessary to remove the isocyanate compound remaining after the reaction on the way out of the system.

The ratio of the amounts of the polymer A and the polyfunctional isocyanate compound (g) used when synthesizing this polyurethane is not particularly limited. For example, the above 2
In the case of stepwise reaction, the molar ratio of the isocyanate group in the compound (g) to the hydroxyl group in the polymer A (NCO / OH)
Is higher than 1, there is no problem, but in order to prevent the molecular weight from increasing at this stage and synthesize polyurethane having a clear block structure, 1.2 to 2.0 is preferable, and 1.
5 to 2.0 is more preferable. Further, the molar ratio of the isocyanate group in the polyfunctional isocyanate compound (g) and the hydroxyl group in the polymer A in the case of the one-step reaction (NCO / OH)
Is preferably 0.5 to 1.5, and 0.8 to
It is more preferably 1.2.

In synthesizing this polyurethane, it is free to use known catalysts such as organic tin compounds and tertiary amines, or use various solvents in order to accelerate the urethanization reaction. Next, a polyester obtained by reacting a polyol component (m) containing the polymer A as an essential component obtained by the production method of the present invention with a compound (i) having two or more carboxyl groups in one molecule explain.

A polyol component (m) containing polymer A as an essential component, which is used when synthesizing this polyester.
Is the same as described above for polyurethane. Further, the compound (i) having two or more carboxyl groups in one molecule is also the same as described above. In addition, in the case of this synthesis, it is free to use a known catalyst such as an inorganic acid such as sulfuric acid or the like for promoting the esterification reaction, or to use various solvents.

When the above-mentioned polyurethane or polyester is used as a molding material, the molding material may further contain other components such as glass fiber, pulp and other fillers, which are contained in conventional molding materials. Release agents, pigments such as calcium carbonate and titanium oxide, ultraviolet absorbers, antioxidants and the like may be included. As a molding method, any conventionally known molding method may be used. Regarding the shape of the molded product, it can be molded into various shapes such as a film shape and a sheet shape.

Next, the block polymer containing the polymer A obtained by the production method of the present invention as an essential component will be described. The method for obtaining this block polymer is not particularly limited, but for example, the following 4 to
There are two methods. Two or more kinds of polyols, which are different kinds of polymer A or a combination of polymer A and another polyol, obtained by the production method of the present invention are used, and these and functional groups capable of reacting with a hydroxyl group are contained in one molecule. A method of reacting with a compound having two or more.

The polymer A obtained by the production method of the present invention is reacted with a polymer having only one hydroxyl group in one molecule and a compound having two or more functional groups capable of reacting with the hydroxyl group in one molecule. How to make. A method of reacting the polymer A obtained by the production method of the present invention with a polymer having one or two or more functional groups capable of reacting with a hydroxyl group in one molecule.

A method of ring-opening polymerization of one or more cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran using the polymer A obtained by the production method of the present invention as an initiator. In the above method, and, as the functional group capable of reacting with a hydroxyl group, is not particularly limited, for example,
Isocyanate group, carboxyl group, triazine ring, methylolated triazine ring, acid anhydride, azlactone ring,
Examples thereof include silanol groups, carbonate groups, epoxy groups, acid halide groups and the like.

The method of the reaction in the above and the above methods is not particularly limited, but for example, any of the one-step reaction method and the multi-step reaction method described in the above description of polyurethane and polyester is used. be able to. The use of this block polymer is not particularly limited, but for example, a surfactant, a compatibilizer, a resin for toner, a hot melt adhesive, a thermoplastic elastomer, a thermosetting elastomer, a resin modifier, an adhesive, Examples include dispersants, heat-resistant transparent resins, impact-resistant transparent resins, artificial leather, synthetic leather, cement water reducing agents, and urethane foam.

The structure of this block polymer is not particularly limited, but is naturally determined according to each application. For example, using surfactant as an example,
It is desirable that the two or more kinds of segments constituting the block polymer are composed of a hydrophilic segment and a hydrophobic segment. In addition, for example, for elastomer use, two or more kinds of segments constituting the block polymer have glass transition temperatures of 10 ° C.
It is desirable that they are different.

[0094]

In the production method of the present invention, the polymerization of the vinyl monomer (a) is carried out in the presence of the alcohols (b) in the initiator system (c) and the non-phosphorus inorganic which essentially require an organic peroxide. The acid (d) is used. Then, hydroxyl groups are easily and reliably introduced into both ends of the polymer produced by polymerization of the vinyl-based monomer (a), and efficiently. Therefore, it becomes possible to efficiently and easily obtain a polymer having hydroxyl groups at both ends from a wide range of vinyl-based monomers including polar vinyl-based monomers easily, inexpensively.

Although the organic peroxide used as an essential component of the initiator system (c) alone cannot introduce hydroxyl groups at both ends of the polymer, the introduction of the hydroxyl group by using the alcohols (b). Will be possible in part. The reason why only a part of the hydroxyl groups can be introduced is that the OR radical generated by the decomposition of the organic peroxide (ROOR) is very unstable, and therefore the hydrogen abstraction reaction (chain transfer reaction)
This is because such side reactions are likely to occur and it is difficult to surely introduce a hydroxyl group at the terminal of the polymer. However, the coexistence of the non-phosphorus inorganic acid (d) further improves the selectivity of the reaction and makes it possible to reliably introduce hydroxyl groups at both ends.

Further, in the production method of the present invention, components other than the above four (a), (b), (c) and (d) are substantially not used. Specifically, (a),
Components other than (b), (c), and (d) are made to be about 10% by weight or less based on the total amount of components. If,
When components (eg, water, solvent, etc.) other than (a), (b), (c), and (d) are used in an amount of more than 10% by weight based on the total amount of components, hydroxyl groups are completely present at one end or both ends. A polymer not containing is produced as a by-product, and the number of terminal hydroxyl groups of the polymer decreases. However, the use of the surfactant (x) in the range of less than 10% by weight with respect to the total amount of components may improve the introduction of hydroxyl groups into the polymer to be produced, but it may not reduce the introduction thereof. There is no problem, so it doesn't matter.

The polymer A obtained by the production method of the present invention is transparent, weather resistant, water resistant, and water resistant by appropriately selecting the kind of the vinyl-based monomer (a) constituting the main chain. Various resins such as polyester resin, polyurethane resin, polycarbonate resin, which are hydrolyzable and chemically resistant, and which are derived from the composition containing the polymer A,
Since it exhibits the properties of various block polymers, etc. that are extremely stretchable (good in bending workability) and tough, they are paints (high solids, low temperature curing, etc.), elastic wall materials, waterproof coating films, Adhesives, floor materials, tackifiers, adhesives, binders (magnetic recording media, ink binders,
Casting binder, baked brick binder, graft material,
Microcapsules, glass fiber sizing, etc.),
Sealant, urethane foam (hard, semi-hard, soft), urethane RIM, UV / EB curable resin, thermosetting elastomer, thermoplastic elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, interface Activator, gel coating agent, artificial marble resin, artificial marble impact resistance imparting agent, ink resin, film (laminate adhesive, protective film, etc.), laminated glass resin, reactive diluent, various molding materials, elasticity It is very useful as a raw material for fibers, artificial leather, synthetic leather, dispersants, aqueous urethane emulsions, and various resin additives and their raw materials.

The polymer A is prepared by reacting the hydroxyl groups at both ends with an appropriate method to obtain another functional group (for example, a polymerizable unsaturated group such as vinyl group, formyl group, amino group,
Carboxyl group, ethynyl group, epoxy group, silanol group, alkoxysilyl group, hydrosilyl group, mercapto group, oxazoline group, maleimide group, azlactone group,
(A lactone group, bromine, chlorine, etc.) can be easily converted into a polymer having both ends. These polymers are also very useful. For example, a polymer having a carboxyl group at both ends (polymer C) is very effective as an impact resistance-imparting agent for epoxy adhesives. In addition, the polymer A
Is a surfactant by adding a plurality of ethylene oxide or propylene oxide to the terminal hydroxyl group,
It is a raw material for urethane foam, cement water reducing agents, compatibilizers, etc.

A composition essentially comprising the polymer A and the polyfunctional isocyanate compound (g), and the polymer A
When using the composition containing the aminoplast resin (h) and the aminoplast resin (h) as essential materials, they are not only flexible and tough, but also have weather resistance, water resistance, hydrolysis resistance, chemical resistance, and hardness. It is possible to obtain a very excellent coating film such as. Further, even if the molecular weight is low, since the hydroxyl group is present at the terminal of the polymer A, the toughness, which is a drawback of the conventional high solid type paint, can be improved.

When the composition containing the polymer A and the polyfunctional isocyanate compound (g) as an essential component was used as an essential component of the sealing material, it was very flexible and tough and was excellent in weather resistance, water resistance and chemical resistance. A sealing material can be obtained. When a composition essentially containing the polymer A and the polyfunctional isocyanate compound (g) is used for urethane foam applications and thermosetting polyurethane elastomer applications, the urethane foam has excellent flexibility, weather resistance, water resistance and chemical resistance. And an elastomer can be obtained.

Both ends obtained by reacting the polymer A with a compound (j) having two kinds of reactive groups of a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group in one molecule are obtained. When a composition containing a vinyl-based monomer having at least one polymerizable unsaturated group in one molecule as an essential component in addition to the polymer B having a polymerizable unsaturated group is used for a gel coat resin composition application In addition, the reaction shrinkage during molding of the gel coat layer is small, the viscosity of the gel coat resin composition during working is low, the workability of the gel coat is good, and the hardness is large, and a tough gel coat layer having good weather resistance is obtained.

Polyurethane obtained by reacting the polymer A with the polyfunctional isocyanate compound (g), and
When the polyester obtained by reacting the polymer A with the compound (i) having two or more carboxyl groups in one molecule is used as an essential component of a molding material, processability, hydrolysis resistance, and weather resistance are obtained. It is possible to obtain a molding material having excellent properties, chemical resistance and low temperature characteristics.

[0103]

EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. Moreover, in the following Examples and Comparative Examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively. —Example 1— 140 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser, and the inside of the flask was replaced with nitrogen. The temperature was raised. After stabilizing the temperature in the reaction vessel, cyclohexanone peroxide 2.0 was added to 40 parts of butyl acrylate and 60 parts of methyl methacrylate.
A mixed solution in which 1 part was dissolved and 0.53 part of hydrochloric acid (35%) and 33 parts of ethylene glycol were simultaneously added dropwise over 1 hour, and then stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. . When the polymerization rate was calculated from the residual rate of butyl acrylate and methyl methacrylate by gas chromatography, it was 85%.

Then, the polymer was extracted and separated from the reaction mixture containing the polymer using a toluene / water-based extraction solvent to obtain a toluene solution containing the polymer. Toluene was distilled off, and the residue was dried at 45 ° C. under reduced pressure to obtain a purified polymer [1]. The number average molecular weight (Mn) of the purified polymer [1] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and was 8500. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [1] is JIS-K-15.
57 based on the OH value determined according to 57 and the value of the number average molecular weight measured above, 3.5 (mol / polymer 1
Mol).

-Example 2-140 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, and the inside of the flask was replaced with nitrogen. Then, while gently blowing nitrogen gas, The temperature was raised to 140 ° C. After the temperature inside the reaction vessel became stable, 1.0 part of cyclohexanone peroxide was added to 40 parts of butyl acrylate and 60 parts of methyl methacrylate.
And a mixed solution of 0.8 parts of AIBN (azobisisobutyronitrile) and 0.53 parts of hydrochloric acid (35%) and 33 parts of ethylene glycol were simultaneously added dropwise over 1 hour. The stirring was continued for 10 minutes at 140 ° C. to complete the polymerization. When the polymerization rate was calculated from the residual rate of butyl acrylate and methyl methacrylate by gas chromatography, it was 89%.

Subsequently, the toluene / water extraction solvent was used to extract and separate the polymer from the reaction mixture containing the polymer to obtain a toluene solution containing the polymer. Toluene was distilled off, and the residue was dried under reduced pressure at 45 ° C. to obtain a purified polymer [2]. The number average molecular weight (Mn) of the purified polymer [2] was measured by the standard polystyrene conversion method using gel permeation chromatography (GPC), and was 11,000. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [2] is JIS-K-1.
Based on the OH value determined according to 557 and the value of the number average molecular weight measured above, the result was 3.2 (mol / polymer 1 mol).

Example 3-140 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, and the inside of the flask was replaced with nitrogen. Then, while gently blowing nitrogen gas, The temperature was raised to 140 ° C. After the temperature inside the reaction vessel became stable, 1.0 part of cyclohexanone peroxide was added to 40 parts of butyl acrylate and 60 parts of methyl methacrylate.
Part and a mixed solution of 0.53 parts of hydrochloric acid (35%), 6
2.8 parts of 0% hydrogen peroxide solution and ethylene glycol 3
After the mixture with 3 parts was dropped simultaneously over 1 hour, 10
Polymerization was completed by continuing stirring at 140 ° C. for one minute. When the polymerization rate was calculated from the residual rate of butyl acrylate and methyl methacrylate by gas chromatography, it was 88%.

Subsequently, the toluene / water extraction solvent was used to extract and separate the polymer from the reaction mixture containing the polymer to obtain a toluene solution containing the polymer. Toluene was distilled off, and the residue was dried under reduced pressure at 45 ° C to obtain a purified polymer [3]. The number average molecular weight (Mn) of the purified polymer [3] was measured by the standard polystyrene conversion method using gel permeation chromatography (GPC), and was 12,000. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [3] is JIS-K-1.
Based on the OH value determined according to 557 and the value of the number average molecular weight measured above, the result was 3.2 (mol / polymer 1 mol).

-Comparative Example 1- 140 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, and the inside of the flask was replaced with nitrogen. Then, while gently blowing nitrogen gas, The temperature was raised to 140 ° C. After stabilizing the temperature in the reaction vessel, cyclohexanone peroxide 2.0 was added to 40 parts of butyl acrylate and 60 parts of methyl methacrylate.
The mixed solution in which parts were dissolved was added dropwise over 1 hour, and then stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. continue,
A purified comparative polymer [1] was obtained by the same purification method as in Example 1.

The number average molecular weight (Mn) of the comparative polymer [1] after purification was determined by gel permeation chromatography (GPC).
As a result of measurement by the standard polystyrene conversion method using
It was 18,000. The average number of terminal hydroxyl groups (Fn (OH)) of the comparative polymer [1] is JIS-K-155.
As a result of calculation based on the OH value obtained according to 7 and the value of the number average molecular weight measured above, it was 0.5 (mol / polymer 1 mol).

Example 4-A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with 320 parts of ethylene glycol (the initial amount of the alcohol (b) charged in the flask), and the flask was purged with nitrogen. After that, the temperature was raised to 140 ° C. while slowly blowing nitrogen gas. After the temperature inside the reactor became stable, 67 parts of butyl acrylate and 4 parts of methyl methacrylate
5 parts and 3 parts of acrylic acid with 4.4 parts of cyclohexanone peroxide dissolved in the first mixture, and hydrochloric acid (35 parts).
%) 1.1 parts was dissolved in 70 parts of ethylene glycol (the amount of alcohols (b) dropped) and 2 parts of the second mixed solution were simultaneously added.
After dropping over a period of time, stirring was continued at 140 ° C. for 30 minutes to complete the polymerization. When the polymerization rate was calculated from the residual rates of butyl acrylate, methyl methacrylate and acrylic acid by gas chromatography, it was 93%.

Then, using a toluene / water-based extraction solvent,
The polymer was extracted and separated from the reaction mixture containing the polymer to obtain a toluene solution containing the polymer. Toluene was distilled off, and the residue was dried at 45 ° C. under reduced pressure to obtain a purified polymer [4]. The number average molecular weight (Mn) of the purified polymer [4] was measured by gel permeation chromatography (GP
The result was 4000 according to the standard polystyrene conversion method using C). The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [4] was calculated based on the OH value determined according to JIS-K-1557 and the value of the number average molecular weight measured above, 3.5 (mol / polymer 1 mol)
Met.

-Examples 5 to 17- In Example 4, the vinyl-based monomer (a), alcohols (b) (initial charge and drop), initiator system (c),
Table 1 shows the type, amount and polymerization temperature of the non-phosphorus inorganic acid (d).
Purified polymers [5] to [17] were obtained in the same manner as in Example 4 except that the steps described in Examples 1 to 4 were performed.

Table 7 shows the properties of these polymers. —Example 18— In Example 4, a vinyl-based monomer (a), alcohols (b) (initial charge and drop), initiator system (c),
Table 5 shows the type, amount and polymerization temperature of the non-phosphorus inorganic acid (d).
In addition, 0.3 part of manganese naphthenate (butyl acrylate solution with a Mn content of 6%) in the initiator system (c) was dissolved in the vinyl monomer (a) to obtain the first mixture. Example except that 2.0 parts of cyclohexanone peroxide was dissolved in 40 parts of ethylene glycol (dropping amount) together with the non-phosphorus inorganic acid (d) and added as a component of the second liquid mixture as a component of the liquid. In the same manner as in 4, a purified polymer [18] was obtained.

The properties of this polymer [18] are shown in Table 7. —Examples 19 to 21— In Example 4, the vinyl-based monomer (a), alcohols (b) (initial charge and drop), initiator system (c),
Table 5 shows the type, amount and polymerization temperature of the non-phosphorus inorganic acid (d).
~ 6 and the surfactant (Example 1
In 9 and 20, 3.0 parts of SPAN60 (manufactured by Kao Corporation, nonionic surfactant), and in Example 21, Perex OT
Purified polymers [19] to [21] were obtained in the same manner as in Example 4 except that -P (manufactured by Kao Corporation, 3.0 parts) was initially charged in the flask.

The properties of these polymers are shown in Table 7. -Example 22-In Example 4, a vinyl-type monomer (a), alcohols (b) (initial charging amount and dropping amount), an initiator system (c),
Table 6 shows the type, amount and polymerization temperature of the non-phosphorus inorganic acid (d).
A purified polymer [22] was obtained in the same manner as in Example 4 except that the above was performed.

The properties of this polymer are shown in Table 7. -Comparative Example 2-In Comparative Example 1, in addition to the mixed solution containing butyl acrylate, methyl methacrylate and cyclohexanone peroxide, a mixed solution prepared by dissolving 0.6 parts of triethylamine in 33 parts of ethylene glycol was used as the mixed solution. Comparative Example 1 except that the solution was dropped into the reaction vessel at the same time over 1 hour
Polymerization was carried out by the same operation as above to obtain a reaction mixture containing a polymer. The polymerization rate of this reaction mixture, which was determined from the residual rate of butyl acrylate and methyl methacrylate by gas chromatography analysis, was as low as 62%.

By performing the same purification treatment as in Example 1 on the above reaction mixture, a purified comparative polymer [2] was obtained. The number average molecular weight (Mn) of this comparative polymer [2] was 6 as measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 000. Further, the average number of terminal hydroxyl groups (Fn (OH)) of the comparative polymer [2] was calculated based on the OH value determined according to JIS-K-1557 and the value of the number average molecular weight measured above. , 0.7 (mol / polymer 1 mol).

Comparative Example 3 In Comparative Example 1, 0.5 part of pyridine was added to ethylene glycol 3 in addition to the mixed solution of butyl acrylate, methyl methacrylate and cyclohexanone peroxide.
Polymerization was performed in the same manner as in Comparative Example 1 except that the mixed solution dissolved in 3 parts was dropped into the reaction vessel simultaneously with the mixed solution over 1 hour to obtain a reaction mixture containing a polymer. The polymerization rate obtained from the residual rate of butyl acrylate and methyl methacrylate by gas chromatography analysis of this reaction mixture was as low as 74%.

By performing the same purification treatment as in Example 1 on the above reaction mixture, a purified comparative polymer [3] was obtained. The number average molecular weight (Mn) of this comparative polymer [3] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 800. Further, the average number of terminal hydroxyl groups (Fn (OH)) of the comparative polymer [3] was calculated based on the OH value determined according to JIS-K-1557 and the value of the number average molecular weight measured above. , 0.7 (mol / polymer 1 mol).

Comparative Example 4 In Comparative Example 1, ethylene glycol 1 was added in the flask.
A purified comparative polymer [4] was prepared in the same manner as in Comparative Example 1 except that 40 parts of SPAN-60 (manufactured by Kao Corporation, nonionic surfactant) was initially charged in an amount of 3.0 parts. ]

The number average molecular weight (Mn) of this comparative polymer [4] was measured by the standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 1000. The average number of terminal hydroxyl groups (Fn (OH)) of the comparative polymer [4] is JIS-K-1557.
Based on the OH value determined according to the above and the value of the number average molecular weight measured above, 0.6 (mol / polymer 1 mol)
Met.

COMPARATIVE EXAMPLE 5 In Example 1, ethylene glycol 1 was added in the flask.
The same polymerization operation as in Example 1 was carried out except that 100 parts of dioxane was initially charged together with 40 parts to produce a comparative polymer [5]. After purifying this comparative polymer [5], its number average molecular weight (Mn) was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and as a result, it was 6000. Also, the average number of terminal hydroxyl groups (Fn (OH)) of the comparative polymer [5]
Is a result calculated based on the OH value determined according to JIS-K-1557 and the value of the number average molecular weight measured above.
It was 5 (mol / polymer 1 mol).

Comparative Example 6 In Example 1, ethylene glycol 1 was placed in the flask.
The same polymerizing operation as in Example 1 was carried out except that 40 parts of toluene and 50 parts of toluene were initially charged to produce a comparative polymer [6]. After purifying this comparative polymer [6], its number average molecular weight (Mn) was measured by the standard polystyrene conversion method using gel permeation chromatography (GPC), and was 6500. The average number of terminal hydroxyl groups (Fn (OH)) of the comparative polymer [6] is
As a result of calculation based on the OH value determined according to JIS-K-1557 and the value of the number average molecular weight measured above, 1.3
(Mol / polymer 1 mol).

Comparative Example 7 In Example 1, ethylene glycol 1 was placed in the flask.
A comparative polymer [7] was produced by performing the same polymerization operation as in Example 1 except that 60 parts of SPAN60 (manufactured by Kao Corporation, nonionic surfactant) was initially charged together with 40 parts. After purification of this comparative polymer [7], its number average molecular weight (Mn) was measured by the standard polystyrene conversion method using gel permeation chromatography (GPC), and was 6600. The average number of terminal hydroxyl groups (Fn (OH)) of the comparative polymer [7] is JIS
-K-1557 was calculated based on the OH value and the value of the number average molecular weight measured above, and the result was 1.5 (mol / mol
The polymer was 1 mol).

Example 23-The polymer [12] 14 obtained in Example 12 was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser.
2 parts, hexamethylene diisocyanate 4.6 parts (NC
O / OH = 1.05 (molar ratio)), 200 parts of toluene and 0.1 part of dibutyltin dilaurate were charged, and 80
The reaction was completed by continuing stirring at 5 ° C for 5 hours to obtain a toluene solution of polyurethane [23].

The number average molecular weight (Mn) of this polyurethane [23] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 14,000. -Example 24-In Example 23, 71 parts of polymer [12] and 58 parts of the polymer [13] obtained in Example 13 were used instead of 142 parts of the polymer [12], and hexamethylene diisocyanate Example 2 except that the amount was changed to 4.4 parts
The same operation as in 3 was performed to obtain a toluene solution of polyurethane [24].

The number average molecular weight (Mn) of this polyurethane [24] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 15,000. -Example 25-In Example 23, it replaced with the polymer [12] 142 parts, except having used 71 parts of polymers [12] and 76 parts of the polymers [13] obtained in Example 13. The same operation as in Example 23 was carried out to obtain a toluene solution of polyurethane [25].

The number average molecular weight (Mn) of this polyurethane [25] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 16000. -Example 26-The same as Example 23 except that 99 parts of polymer [12] and 0.71 part of 1,4-butanediol were used in place of 142 parts of polymer [12] in Example 23. Was performed to obtain a toluene solution of polyurethane [26].

The number average molecular weight (Mn) of this polyurethane [26] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 15,000. -Example 27- Methyl ethyl ketone 100 was put into a flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, a dropping funnel, and a reflux condenser.
And 2.0 parts of hexamethylene diisocyanate were charged and heated to a temperature at which reflux was applied (about 80 ° C.), then 60 parts of Byron GK130 (polyester diol, manufactured by Toyobo Co., Ltd., Mn = 6000) and Dibutyltin dilaurate 0.1 part with methyl ethyl ketone 20
What was dissolved in 0 part was added dropwise over 1 hour, and stirring was continued at the above temperature for 3 hours to complete the reaction, to obtain a methyl ethyl ketone solution of polyester having isocyanate groups at both ends.

Next, the polymer [1 obtained in Example 13
3] 82 parts and 0.1 parts of dibutyltin dilaurate dissolved in 100 parts of methyl ethyl ketone were placed in a flask containing the methyl ethyl ketone solution obtained above.
The mixture was added dropwise over a period of time, and stirring was continued at the reflux temperature for 3 hours to complete the reaction, to obtain a methyl ethyl ketone solution of polyurethane [27].

The number average molecular weight (Mn) of this polyurethane [27] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 28,000. -Example 28- A flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, a dropping funnel and a reflux condenser was charged with 100 parts of toluene and 3.5 parts of hexamethylene diisocyanate, heated to 80 ° C, and then there. The polymer obtained in Example 13 [1
3] 71 parts and 0.1 part of dibutyltin dilaurate dissolved in 100 parts of toluene were added dropwise over 1 hour, and the mixture was further stirred at the above temperature for 3 hours to complete the reaction, and an isocyanate group was added to both ends. A toluene solution of the polymer having was obtained.

Next, the polymer [1 obtained in Example 12
2] A solution prepared by dissolving 112 parts and 0.1 part of dibutyltin dilaurate in 100 parts of toluene was added dropwise to the flask containing the toluene solution obtained above over 1 hour,
Further, stirring was continued at 80 ° C. for 3 hours to complete the reaction, and a toluene solution of polyurethane [28] was obtained. The number average molecular weight (Mn) of this polyurethane [28] was measured by the standard polystyrene conversion method using gel permeation chromatography (GPC) and found to be 15,000.

-Example 29- The polymer [12] 142 obtained in Example 12 was placed in a flask equipped with a stirrer, a thermometer, an azeotropic dehydration tube and a reflux condenser.
Parts, 3.9 parts of phthalic anhydride, and 5 parts of xylene were charged, and the mixture was thoroughly stirred and dehydrated from the azeotropic dehydration tube while
2 hours at 00 ° C, then 2 hours at 160 ° C and finally 22
The reaction was carried out at 0 ° C. for 1 hour to obtain polyester [29].

The number average molecular weight (Mn) of this polyester [29] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 13000. Example 30 In Example 29, 65 parts of the polymer [12] and 53 parts of the polymer [13] obtained in Example 13 were used instead of 142 parts of the polymer [12], and phthalic anhydride Amount 3.
Polyester [30] was obtained by performing the same operation as in Example 29 except that the amount was changed to 6 parts.

The number average molecular weight (Mn) of this polyester [30] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 15,000. Example 31 In Example 29, 71 parts of the polymer [12] and 76 parts of the polymer [13] obtained in Example 13 were used in place of 142 parts of the polymer [12], and phthalic anhydride Amount 3.
Polyester [31] was obtained in the same manner as in Example 29 except that the amount was changed to 5 parts.

The number average molecular weight (Mn) of this polyester [31] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 18,000. -Example 32-The same as Example 29 except that 92 parts of polymer [12] and 0.8 part of 1,4-butanediol were used in place of 142 parts of polymer [12] in Example 29. Was carried out to obtain polyester [32].

The number average molecular weight (Mn) of this polyester [32] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 14,000. -Example 33- Resin for acrylic primer (composition (%): ethyl acrylate / styrene / butyl acrylate / methacrylic acid / 2-hydroxyethyl acrylate / methyl methacrylate =)
35/35/12/8/6/3, number average molecular weight 1500
0, hydroxyl value 36, acid value 50) to 100 parts of alkyl ether amino formaldehyde resin, Cymel 325 (manufactured by Mitsui Cyanamid Co., Ltd.), paratoluenesulfonic acid 0.25 part as a curing accelerator, rust preventive pigment As zinc chromate as a solvent, 400 parts of cyclohexanone as a solvent and 50 parts of titanium oxide were well stirred and mixed, and chromated in advance to 0.5 mm
It was applied to a thick galvanized steel sheet with a bar coater so that the dry film thickness was 5 μm, and baked at 220 ° C. for 1 minute.

After cooling, on the primer coating film, 132 parts of the polymer [4] obtained in Example 4, 30 parts of Cymel 325 (manufactured by Mitsui Cyanamid Co., Ltd.) as an alkyl etherified aminoformaldehyde resin, and a curing accelerator were used. 0.25 parts of paratoluene sulfonic acid, 125 parts of titanium oxide,
Leveling agent MK Conc (Kyoeisha Oil and Fat Chemical Co., Ltd.)
0.5 parts) and 400 parts of cyclohexanone were mixed well with a paint shaker with a dry film thickness of 25.
A coated steel sheet was produced by applying a bar coater so that the thickness became μ, setting at 70 ° C. for 10 minutes, and then baking at 235 ° C. for 60 seconds. And about the coating film,
The coin scratchability was evaluated by the method (1) below.

[0140] Further, chromate-treated 0.
132 parts of the polymer [4] obtained in Example 4, 30 parts of Cymel 325 (manufactured by Mitsui Cyanamid Co., Ltd.) as an alkyl etherified aminoformaldehyde resin, and para-toluene as a curing accelerator were applied to a 5 mm thick galvanized steel sheet. 0.25 parts of sulfonic acid, 125 parts of titanium oxide, leveling agent MK Conc (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) 0.5
Parts and 400 parts of cyclohexanone were well mixed by stirring with a paint shaker, and were directly applied with a bar coater so as to have a dry film thickness of 25 μm without using the above acrylic primer resin and set at 70 ° C. for 10 minutes. Then, it baked at 235 degreeC for 60 second, and produced the coated steel plate. And about the coating film, the following (2)-
The evaluation of (6) was performed. (1) Coin scratch-resistant coated steel sheet The coating film state was visually evaluated after the coating film was strongly scratched with a 10-yen coin.

∘: The primer did not peel off from the base material (steel plate), the interlayer adhesion between the primer and the top coat was good, and only the top coat was cohesively broken. ◯: The primer is slightly peeled from the substrate, but the interlayer adhesion between the primer and the top coat is good. B: The primer does not peel off from the substrate, but the interlayer adhesion between the primer and the topcoat is poor and the topcoat easily peels off.

X: The top coat is peeled off from the substrate together with the primer. Inadequate adhesion of primer to substrate. XX ... The top coat with the primer peels off significantly from the substrate. (2) Room temperature workability (T vent) At room temperature, the coated steel sheet was sequentially bent from 4 degrees to 180 degrees, and cracks generated in the bent portion were observed and judged with a magnifier of 15 times. For example, if a bending occurs when three copper plates with the same plate thickness are sandwiched and bent, and cracks occur, the workability is said to be T-vent 3T. Therefore, the smaller the T-vent number, the better the workability. Is shown. (3) Adhesion property A cross-cut first-eye peeling test was performed according to JIS D-0202. (4) Boiling Water Resistance Test The coated steel sheet was immersed in ion-exchanged water, boiled for 8 hours, then taken out, and the coating film was observed and judged.

B: No blister. Adhesion 100/100 according to (3) above. △: Blister occurred. ×: Remarkably blister occurred. (5) Cross-cut with touch knife coated steel plate with a cutter knife
After performing a salt spray test for 500 hours according to SK-5400, cellophane tape was peeled from the cross cut portion, and the peel width was evaluated. (6) Pencil hardness It was performed according to JIS K-5400 using a Mitsubishi Uni-Pencil.

The test results are summarized in Table 8. As shown in Table 8, the top coat using the polymer [4] obtained in Example 4 has excellent adhesion to the primer, is not easily scratched, is flexible and has excellent processability, and is resistant to It was found that it also has excellent boiling water and touch resistance. -Comparative Examples 8 and 9-In Example 33, the same operation as Example 33 was repeated except that the polymer shown in Table 8 was used instead of the polymer [4] as the polymer used for the coating material for the top coat. Then, a coated steel sheet for comparison was prepared. The coating films of these coated steel sheets for comparison were subjected to the same evaluation test as in Example 33, and the results are summarized in Table 8.

Example 34 To 107 parts of the polymer [22] obtained in Example 22, 26 parts of xylene and 26 parts of butyl acetate were added and well stirred to prepare a polymer solution, which was further added thereto. Titanium oxide (Taipec R-820, manufactured by Ishihara Sangyo Co., Ltd.) was used as the pigment concentration of 40
% So as to be well dispersed in a sand mill to obtain a dispersion liquid (hereinafter referred to as liquid I). Next, polyfunctional isocyanate (Sumijour N, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was weighed in an amount of 1: 1 with respect to the hydroxyl group in the above-mentioned liquid I, and this was used as liquid II. In this way, a two-component urethane resin coating composition comprising liquid I and liquid II was obtained.

By mixing the liquid I and liquid II of this coating composition,
The obtained mixed liquid was applied to a zinc-phosphide-treated plate by air spraying so as to have a dry film thickness of 40 μm, and then forcibly dried at 60 ° C. for 30 minutes to prepare test pieces for various performance tests. The performance of the coating film of this test piece was evaluated by the following performance test method in four grades of ⊚ to ∘ to ∘ to x except for the pencil hardness. The evaluation results are shown in Table 9. (Performance evaluation method) Dryability: Evaluation by acupressure and masking test immediately after forced drying. Gloss: Comparison of 60-degree specular reflectance measurement values. Persistence: Visual judgment of coating film. Adhesion: Judged by the adhesion to the coated substrate. Pencil hardness: Scratch strength with Mitsubishi Uni-Pencil. Workability (T-vent): The coated steel sheet was sequentially bent from 180 degrees 4T to 0T, and cracks generated in the refracted portion were observed and judged with a magnifier of 15 times. For example, if a bending occurs when three copper plates of the same plate thickness are sandwiched and bent, and cracking occurs, the workability is said to be T-vent 3T. Therefore, the smaller the T-vent number, the better the workability. Is shown. Solvent resistance in the initial stage of curing: Judgment by spot test of thinner for urethane. Chemical resistance: 5% NaOH aqueous solution and 5% diluted acid, soaked for 24 hours. Weather resistance (chalking resistance): Evaluation by gloss retention rate after outdoor exposure. Weather resistance (contamination resistance): Judged by the degree of stains on the coating film after outdoor exposure. Spray workability: Judged by the workability during spraying. Solvent dilutability: Judged by the degree of ease of dilution with thinner.

Comparative Example 10 In Example 34, instead of the polymer [22], the monomer composition was styrene / cyclohexyl methacrylate / 2-hydroxyethyl methacrylate / methyl methacrylate / methacrylic acid = 40/30/20. The same procedure as in Example 34 was carried out except that a copolymer having a number average molecular weight (Mn) of 2600 at / 10/2 (weight ratio) (comparative polymer [10]) was used. A coating composition containing the combination [10] was prepared. A performance evaluation test of a coating film using this coating composition was performed in the same manner as in Example 34. The results are shown in Table 9.

-Example 35- The polymer obtained in Example 5 was prepared by adding 3 equivalents of tolylene diisocyanate to trimethylolpropane (Coronate L (manufactured by Nippon Polyurethane Company, hereinafter abbreviated as Coronate L)). [5] 5 parts was mixed with 139 parts and diluted with ethyl acetate to a 20% solution to obtain an adhesive solution.
As the adherend, a polyerylene terephthalate film having a thickness of 12 μm (hereinafter abbreviated as “PET”) and an unstretched polypropylene film having a thickness of 50 μm subjected to corona discharge treatment (hereinafter abbreviated as “CPP”) are used. In order to laminate the above, both of them were coated with the above adhesive solution by a dry laminator so as to have a solid content of 3.0 g / m ² , the solvent was volatilized, and then they were laminated. At that time, the wetting property of the adhesive solution was examined. The obtained laminated film was cut into a test piece having a width of 15 mm, and a T-type peeling test was performed with a tensile tester at 300 mm / min to measure the initial adhesive force. Also, after pasting, 5
A test piece was prepared from a laminate film obtained by curing at 0 ° C. for 3 days, and the normal state adhesive strength, hot water resistance, chemical resistance and flexibility were evaluated by the following methods. The results are shown in Table 10. (1) Normal-state adhesive strength A T-type peel test similar to the initial adhesive strength was performed. (2) Hot water resistance and chemical resistance In the hot water resistance test, the test piece was put together with water in a 50 cc autoclave, treated at 120 ° C. for 5 hours, and then subjected to a T-type peel test to examine the peeled state and strength.

In the chemical resistance test, the test piece was placed at 25 ° C. for 4 hours.
The T-type peeling test was performed on the one immersed in the 4% acetic acid aqueous solution. (3) Flexibility The flexibility was judged by the state of peeling in each of the above peeling tests. The meanings of the marks in the table are as follows.

◯: Peel strength is large and peeling occurs, and thus uniform strength is exhibited. Δ: Partially strong, but easily peeled off. X: Peeling strength is small and easily peeled off. (4) Wetting characteristics (observation results) ◯: Uniform application is possible.

Δ: Repels partially. X: Repels. From the above test results, the polymer [5] obtained in Example 5 was obtained.
When used as an adhesive for laminating, the adhesive composition using is not only strong in initial and normal adhesive strength, but also very excellent in hot water resistance, chemical resistance and flexibility. It was confirmed.

Comparative Examples 11 and 12 The procedure of Example 35 was repeated except that the polymer shown in Table 10 was used in place of the polymer [5] in Example 35 to obtain a comparative laminated film. A test piece was obtained. Table 10 shows the evaluation results of the normal-state adhesive strength, hot water resistance, chemical resistance, flexibility and wettability of each test piece.

-Example 36- 41 parts of the polymer [6] obtained in Example 6 was mixed with ethyl acetate 3
After adding 5 parts, 30 parts of toluene, and 0.5 parts of Coronate L (isocyanate compound manufactured by Nippon Polyurethane Co.) and stirring well, the thickness after drying was 25 μm on a 25 μm-thick PET film. Apply and 3 at 100 ℃
A pressure-sensitive adhesive sheet was obtained by heat-drying for minutes.

With respect to this pressure-sensitive adhesive sheet, the adhesive force at 23 ° C. and 5 ° C., the initial tack (probe tack) and the adhesive holding force were measured by the following methods. The results are shown in Table 11. Adhesive strength : Test pressure-sensitive adhesive sheet (25 ° C) in an atmosphere having a temperature of 23 ° C and a humidity of 65% and in an atmosphere having a temperature of 5 ° C.
mm width) is laminated on a polyethylene plate by reciprocating a 2 kg rubber roller once. After 25 minutes, the resistance value when peeled off at a speed of 300 mm / min in the 180 degree direction was measured.

Initial tack (probe tack) : Temperature is 2
Attach the test pressure-sensitive adhesive sheet to a probe tack tester (manufactured by Nichiban Co., Ltd.) in an atmosphere with a humidity of 3% and a humidity of 65% and a temperature of 5 ° C, and a contact time of 1 second and a speed of 1 cm / second. The resistance value when peeled off was measured. Adhesive holding power : A test pressure-sensitive adhesive sheet is attached to a stainless steel plate (SUS304) in an area of 25 mm x 25 mm, and 20
After a lapse of minutes, a load of 1 kg was applied at 80 ° C., and the time until falling was measured.

Example 37-119 parts of the polymer [7] obtained in Example 7, 15 parts of ethyl acetate, 15 parts of toluene, 3.5 parts of hexamethylene diisocyanate, Coronate L (isocyanate compound manufactured by Nippon Polyurethane Co., Ltd.) ) 0.5 part and 0.1 part of dibutyltin dilaurate were added and well stirred, and then coated on a 25 μm-thick PET film so that the thickness after drying would be 25 μm, and heated at 100 ° C. for 3 minutes. It was dried to obtain a pressure-sensitive adhesive sheet.

About this pressure-sensitive adhesive sheet, Example 36
Adhesive force at 23 ° C. and 5 ° C., initial tack (probe tack), and adhesive holding force were measured by the same method as described in 1. The results are shown in Table 11. As shown in Table 11, a pressure sensitive adhesive composition using the polymer [6] obtained in Example 6 and a pressure sensitive adhesive composition using the polymer [7] obtained in Example 7 It was confirmed that each of them was excellent not only in adhesive strength at room temperature, probe tack and adhesive holding strength, but also in adhesive strength and probe tack especially at low temperature.

Comparative Example 13 The procedure of Example 36 was repeated except that the copolymer shown in Table 11 was used instead of 41 parts of the polymer [6] in Example 36, and the feeling for comparison was obtained. A pressure-bonded sheet was obtained.
With respect to this pressure-sensitive adhesive sheet for comparison, the adhesive force at 23 ° C. and 5 ° C., the initial tack (probe tack), and the adhesive holding force were measured in the same manner as in Example 36. The results are shown in Table 11.

-Example 38- 147 parts of the polymer [8] obtained in Example 8 was added with 100 parts of calcium carbonate, 15 parts of titanium dioxide and 2 parts of calcium oxide.
0 copies, Disparon 3600N (Kusumoto Kasei Co., Ltd.) 2
Parts, 0.5 parts of dibutyltin dilaurate and 0.2 parts of carbon black are mixed and well stirred with a kneader, then 9.5 parts of hexamethylene diisocyanate is added, and well stirred with a kneader at 80 ° C. for 3 hours. Thus, an elastic sealant was obtained. When this elastic sealant was subjected to the characteristic evaluation according to JIS-A5757 and the weather resistance test shown below, the results shown in Table 12 were obtained. Weather resistance test : In the sunshine weather meter,
Atmosphere temperature 63 ° C, under UV irradiation, 1 cycle 2 hours, 1
Preliminarily prepared test piece (dumbbell) was allowed to stand under the condition of rainfall for 18 minutes during the cycle, and after 160 hours, the test piece (dumbbell) was taken out and its elongation retention rate (%)
Was measured. The elongation retention was determined by the ratio of the maximum elongation before and after the weather resistance test. The results are shown in Table 12.

As shown in Table 12, the elastic sealant composition using the polymer [8] obtained in Example 8 has not only excellent elongation in the normal state but also excellent weather resistance. It was confirmed that it was a thing. -Comparative Examples 14 to 16-In Example 38, the same operation as in Example 38 was repeated except that the polymer shown in Table 12 was used instead of the polymer [8] to obtain each comparative elastic sealant. It was

For these comparative elastic sealants,
When a performance test similar to that of the polymer 38 was conducted, the results shown in Table 12 were obtained. -Example 39-The polymer obtained in Example 9

[9] A mixture of 980 parts and 6.1 parts of trimethylolpropane was dried by heating at 70 ° C. for 2 hours under a reduced pressure of 2 Torr. Isolate to the dried and degassed polyol mixture.
143-L (Upjohn Polymer Chem
icals) 500 parts (isocyanate 2.56 meq / g) were added and the temperature was kept at 70 ° C. for 70 minutes to complete the reaction. The product has an isocyanate content of 2.2 meq / g and 2000 at 25 ° C.
It was an almost colorless liquid with a viscosity of 0 cps.
When it was stored at 80 ℃ for 2 weeks, it was 400 ℃ at 25 ℃.
The viscosity increased to 00 cps.

Next, 80 g of the above product heated to 35 ° C.
Is 100 ml of a 2% aqueous solution of Pluronic L-62, which is a nonionic surfactant manufactured by Wyandotte.
By vigorously stirring together with it, a flexible and supple flexible urethane foam was obtained. The physical properties are shown in Table 13. -Comparative Examples 17 to 19-Polymer in Example 39

[9] The same operation as in Example 39 was repeated, except that the types and amounts of the polymers shown in Table 13 were used instead of 980 parts, to give flexible urethane foams for comparison. The physical properties thereof are shown in Table 13.

-Example 40- (Synthesis of Polymer Having Polymerizable Unsaturated Groups at Both Terminals) The polymer [10] 137 obtained in Example 10 was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. Parts, maleic anhydride 5.8 parts, dibutyltin oxide 0.1 parts, hydroquinone 0.1 parts and toluene 200 parts were charged.
After stirring the mixture at 0 ° C. for 5 hours to carry out the reaction, the toluene was removed by an evaporator and a vacuum dryer.
A polymer [40] was obtained.

Example 41- (Synthesis of Polymer Having Polymerizable Unsaturated Groups at Both Terminals and Side Chains) The polymer obtained in Example 11 was added to a flask equipped with a stirrer, a reflux condenser and a thermometer. 11] 158 parts, 2-isocyanatoethyl methacrylate 18 parts, dibutyltin dilaurate 0.1 part, hydroquinone 0.1 part and toluene 200 parts were charged, and the reaction was carried out by stirring at 80 ° C. for 5 hours and then the evaporator. Then, toluene was removed with a vacuum dryer to obtain a polymer [41].

-Examples 42 to 46-The polymers [40] and [41] obtained in Examples 40 and 41 were used to prepare gel coat resin compositions in the formulations and amounts shown in Table 14. Aerosil # 200 for each 100 parts of these gel coat resin compositions
2.5 parts (thixotropic agent, manufactured by Nippon Aerosil Co., Ltd.), 0.015 parts as a metal component of cobalt naphthenate, 1.0 part of 55% methyl ethyl ketone peroxide (Permeric N, manufactured by NOF CORPORATION) may be added. After mixing, the mixture was pneumatically compressed with a spray gun having a caliber of 3.0 mm.
It was applied to a glass plate so that the applied film thickness was 0.2 to 0.3 mm at 0 kg / cm ² . Next, this was cured at 60 ° C. for 2 hours, then allowed to cool to room temperature, and a glass fiber reinforced plastic layer was molded and cured using an unsaturated polyester resin and glass fiber on the obtained coating film. It was Then, the molded product was released from the glass plate to obtain a molded product having a gel coat resin layer.

The coating film physical properties and weather resistance of the gel coat layer of this molded product were measured as follows, and the results are shown in Table 14.
Summarized in. (1) Viscosity, thixotropy and gel time It was carried out according to JIS 6901 liquid unsaturated polyester resin test method. (2) Visual appearance of the film- forming spray coating (repellency) was judged visually. (3) Pencil hardness A Mitsubishi Uni-Pencil was used to perform the test according to JIS K-5400. (4) Weather resistance (blister generation time) Using a Sunshine Weatherometer manufactured by Suga Test Instruments Co., Ltd., a sample molding was prepared under the conditions of an atmospheric temperature of 65 ° C., a spray cycle of 18 minutes / 120 minutes, and a light source of arc carbon.
Gloss of surface gel coat layer (000 hours)
(Gloss) retention rate was determined.

As can be seen from Table 14, the gel coat resin compositions of Examples 42 to 46 have no sagging when applied to various molded products, have a low viscosity during work and have good workability. It was confirmed that a gel coat layer having high hardness and good weather resistance was formed. -Examples 47 to 49-Polyurethane [24] obtained in Example 24, Example 2
Each of the polyurethane [28] obtained in Example 8 and the polyester [30] obtained in Example 30 was subjected to the following evaluation test on the thermoplastic elastomer.
The results are shown in Table 15. (1) Tensile elongation test It was conducted according to JIS-K6301 using a No. 3 dumbbell. (2) Oil resistance test The polymer was immersed in JIS # 3 oil at 100 ° C. for 70 hours, and the volume change rate (%) of the polymer after the immersion was measured before the test. (3) Weather resistance test In a sunshine weather meter, dumbbells melt-cast at 200 ° C. were allowed to stand under the conditions of 63 ° C. ambient temperature, UV irradiation for 1 cycle 2 hours, and rainfall for 18 minutes during 1 cycle. , After 24 hours and 330
Take out the dumbbell after a while and hold its elongation (%)
Was measured. The elongation retention was determined by measuring the tensile elongation at break according to JIS-K6301 and determining the ratio before and after the weather resistance test. (4) Chemical resistance test A No. 3 dumbbell was used for the test according to JIS-K6301. The polymer was immersed in a 40% NaOH aqueous solution and each solvent at 23 ° C. for 5 days, and then the polymer was taken out and the surface state thereof was observed. The chemical resistance was graded from the surface condition to the following A to D.

A: No change at all. B: Almost no change. C: The surface slightly expands. D: It becomes brittle when expanded. As shown in Table 15, the thermoplastic elastomers using the polyurethanes and polyesters of Examples have not only a large elongation in a normal state but also very excellent oil resistance, weather resistance, chemical resistance and the like. It was -Comparative Examples 20 and 21-The comparative polymers shown in Table 15 were evaluated in the same manner as in Examples 47 to 49 for thermoplastic elastomers. The results are shown in Table 15.

-Examples 50 and 51-The polyurethane [25] obtained in Example 25 and the polyester [31] obtained in Example 31 were subjected to an evaluation test on the following molding materials, and the results are shown in Table 16.
Summarized in. (1) Temperature dependence of melt flow characteristics of moldable polyurethane and polyester was measured by a temperature rising method using a drop-down flow tester (hold 185 ° C. × 5 min, heating rate 5 ° C./min, die diameter × length =). 0.5mmφ × 5mmL, load 20kg)
By measuring the viscosity with, the logarithmic value of the flow rate ratio correlated with the absolute temperature is plotted against the reciprocal of the absolute temperature based on the result, and the slope K is obtained. Apparent activation energy E of flow
a (Kcal / mol) was calculated and evaluated.

Ea = −2.303 R · K [where R represents a gas constant (= 1.987 cal / deg · mol)] The flow rate ratio = (amount of polymer flowing out from the flow tester per unit time at the measurement temperature) / (amount of polymer flowing out from the flow tester per unit time at the reference temperature). (2) Low temperature characteristics For low temperature characteristics, polyurethane or polyester pellets are pressed at 250 ° C for 2 minutes (10 kg / cm 2).
A film having a thickness of 100 μm was prepared by pressing and evaluated by measuring a main dispersion peak temperature (Ta) by a dynamic viscoelasticity automatic measuring machine (110 Hz). (3) Hydrolysis resistance The hydrolysis resistance was evaluated by the jungle test. Jungle test is 50μ at 70 ℃ and 95% relative humidity.
3 m thick polyurethane or polyester film
The film was allowed to stand for 0 day and evaluated by the tensile strength retention rate of the film before and after the jungle test. (4) Weather resistance test In a weather meter, the atmospheric conditions were set to 40 ° C. and humidity 68%, and a polyurethane or polyester film having a thickness of 50 μm was irradiated with light, and after 7 days, the film was taken out and subjected to a weather resistance test. Front and rear tensile strength retention rate (%)
I asked.

As shown in Table 16, the molding materials using the polyurethanes and polyesters of Examples have good molding processability and excellent not only low temperature characteristics but also excellent hydrolysis resistance and weather resistance. It was confirmed to be excellent. -Comparative Examples 22 and 23-For the comparative polymers shown in Table 16, evaluation tests on molding materials were carried out in the same manner as in Examples 50 to 51. The results are shown in Table 16.

-Example 52- (Example relating to artificial leather composition and synthetic leather composition)
The polymer [12] 14 obtained in Example 12 was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser.
2 parts, 1,4-butanediol 10 parts, TDI NCO
/OH=1.05 (molar ratio), and then 0.1 part of dibutyltin dilaurate was added, and the reaction was completed by continuing stirring in DMF at 80 ° C. for 5 hours to give polyurethane [52]. Obtained.

The number average molecular weight (Mn) of this polyurethane [52] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 13000. TH this polyurethane [52]
It was redissolved in F to form a film. -Comparative Example 24-(Comparative example regarding artificial leather composition and synthetic leather composition)
The procedure of Example 52 was repeated except that a conventionally known polyester diol having a number average molecular weight (Mn) of 2000 was used in place of the polymer [12] to obtain a comparative polyurethane [24]. Obtained.

-Comparative example 25- (Comparative example concerning artificial leather composition and synthetic leather composition)
The same operation as in Example 52 was repeated except that a conventionally known polyether diol having a number average molecular weight (Mn) of 3000 was used in place of the polymer [12] in Example 52, and a comparative polyurethane [25] Got

-Example 53 and Comparative Examples 26-27- (Evaluation test for artificial leather composition and synthetic leather composition) The polyurethane [52] obtained in Example 52 and the comparison obtained in Comparative Examples 24-25. Polyurethane [2
For 4] to [25], the following evaluation tests were performed on artificial leather and synthetic leather. (1) Hydrolysis resistant polyurethane [52] and comparative polyurethane [2]
4] was evaluated by the jungle test. In the jungle test, a polyurethane film with a thickness of 50 μm was left for 12 days at 70 ° C. and 95% relative humidity, and the tensile strength retention rate (%) of the film was calculated from the stress-strain characteristic results by Instron before and after the jungle test. Evaluated.
The results were as follows.

Polyurethane [52] ... 95% Comparative polyurethane [24] ... 76% (2) Heat resistance The heat resistance of polyurethane [52] and comparative polyurethane [25] was evaluated. The heat resistance was evaluated by allowing each polyurethane film to stand under hot air drying at 120 ° C. for about 6 days, and obtaining the tensile strength retention rate (%) of the film from the results of stress-strain characteristics by Instron before and after the hot air drying. The results were as follows.

Polyurethane [52] ... 93% Comparative polyurethane [25] ... The shape of the film was not retained. -Example 54- (Example relating to printing ink composition) 1220 parts of the polymer [14] obtained in Example 14 and isophorone diisocyanate 66 were placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. Add 7 parts and mix, 95 ° C
And reacted for 10 hours to obtain a urethane prepolymer having a free NCO of 1.5%. Methyl ethyl ketone (ME
K) 620 parts was added to make a uniform solution. Then, 23.3 parts of isophorone diamine and di-n-butylamine 2.
To a solution prepared by dissolving 4 parts in a mixed solution of 226 parts of MEK and 118 parts of isopropanol, 1447 parts of the MEK solution of the urethane prepolymer obtained above was added dropwise at room temperature. After the dropping, the temperature was raised and the mixture was reacted at 50 ° C. for 3 hours to obtain a polyurethane solution.

After 37.5 parts of this polyurethane solution, 25 parts of titanium oxide and 23 parts of MEK were placed in a ball mill for 24 hours, 29 parts of ethyl acetate were added to obtain a printing ink composition. This ink composition is used to print on a nylon film and a polyester film with a gravure printer, and the printability (adhesiveness and blocking resistance) and durability (hydrolysis resistance and heat deterioration resistance) are determined by the methods shown below. I checked. The results are shown in Table 17. This printing ink composition had good viscosity and no change in viscosity even after long-term storage. (1) Printability Adhesiveness (Cellotape Adhesiveness): It is left for one day after printing, a cellophane tape is attached to the printed part, and this is rapidly peeled off.

Good ... It does not come off at all. Defective ... Partly peeled off. Blocking resistance: 2 when the printed surfaces of two prints are matched
After stacking the sheets and tightening them so that the printed surfaces were in close contact with each other with a heat press and leaving them at 40 ° C. for 24 hours, the printed materials were peeled off from each other.

Good ... Peeled without any feeling of resistance. Slightly good ... There is a slight resistance. Defective: Something that has a clear resistance, or something that does not come off. (2) Durability Hydrolysis resistance: The printed matter was immersed in hot water at 100 ° C. for 72 hours, and the tackiness of the printed portion was examined.

Good ... No tackiness. Poor ... adhesive. Heat deterioration resistance: The printed matter was left in a hot air dryer at 120 ° C. for 1 week, and then the tackiness of the printed portion was examined.

Good ... No tackiness. Poor ... adhesive. -Comparative Example 28- (Comparative Example for Printing Ink Composition) In Example 54, 300 parts of conventionally known polytetramethylene glycol having a number average molecular weight (Mn) of 2,000 was used in place of the polymer [14]. Except for the above, the same operation as in Example 54 was repeated to obtain a comparative printing ink composition, and this composition was examined for printability and durability by the same method as in Example 54. The results are shown in Table 17.

-Comparative Example 29- (Comparative Example for Printing Ink Composition) In Example 54, 300 of polybutylene adipate diol having a conventionally known number average molecular weight (Mn) of 2,000 was used in place of the polymer [14]. Parts and 4,4-dicyclohexylmethane diisocyanate were used, except that the same operation as in Example 54 was repeated to obtain a comparative printing ink composition, which was prepared in the same manner as in Example 54. , Printability and durability were investigated. The results are shown in Table 17.

-Example 55- (Example relating to thermosetting polyurethane elastomer composition) Next, in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, the polymer obtained in Example 15 [ 15] 4230 parts, butanediol 51 parts and T
DI (397 parts) was added, and the mixture was stirred and reacted at 80 ° C. for 3 hours in a nitrogen stream.

4678 parts of the obtained reaction product were degassed under reduced pressure at 80 ° C. and melted at 120 ° C. in advance3.
284 parts of 3'-dichloro-4,4'-diaminodiphenylmethane was added, and the mixture was stirred for 1 minute so as not to involve bubbles, and then poured into a mold heated to 100 ° C, and 100 ° C.
After curing for 24 hours, polyurethane [55] was obtained.
The stress-strain characteristics (using an Instron tester) and durability of this polyurethane [55] were examined. The durability was evaluated by the hydrolysis resistance and heat resistance shown below. The results are shown in Table 18. (1) The hydrolysis resistance was evaluated by the jungle test. In the jungle test, the polyurethane molded product was allowed to stand for 12 days under the conditions of a temperature of 70 ° C and a relative humidity of 95%, and the tensile strength retention ratio of the molded product was determined from the stress-strain characteristic results by the Instron tester before and after the jungle test. evaluated. (2) The heat-resistant urethane film was allowed to stand under hot air drying at 120 ° C. for about 6 days, and the tensile strength retention rate of the film was evaluated based on the stress-strain characteristic results obtained by the Instron tester before and after the hot air drying.

Comparative Example 30- (Comparative Example Concerning Thermosetting Polyurethane Elastomer Composition) In Example 55, 552 parts of a conventionally known polyester diol having a number average molecular weight (Mn) of 1000 was used in place of the polymer [15]. The same operation as in Example 55 was repeated except that it was used to obtain a comparative polyurethane [30].

The stress-strain characteristics and durability of this comparative polyurethane [30] were examined in the same manner as in Example 55. The results are shown in Table 18. -Comparative Example 31- (Comparative Example for Thermosetting Polyurethane Elastomer Composition) In Example 55, 552 parts of a conventionally known polyether diol having a number average molecular weight (Mn) of 1000 was used in place of the polymer [15]. Except for the above, the same operations as in Example 55 were repeated to obtain a comparative polyurethane [31].

The stress-strain characteristic and durability of this comparative polyurethane [31] were examined in the same manner as in Example 55. The results are shown in Table 18. -Example 56- (Synthesis of polyurethane prepolymer having isocyanate groups at both ends) The polymer [12] obtained in Example 12 was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. By adding 128 parts and 8.3 parts of tolylene diisocyanate and stirring the mixture in a nitrogen stream at 80 ° C. for 3 hours to cause a reaction, an isocyanate-terminated polyurethane prepolymer [56] was obtained.

-Example 57- (Example relating to resin composition for flooring material) Isocyanate-terminated polyurethane prepolymer [5 obtained in Example 56
6] is used to produce a polyurethane composition having the composition shown in Table 19 (resin composition for flooring materials).
The hardness, surface tackiness, and durability (hydrolysis resistance and heat resistance) were measured and evaluated. The results are shown in Table 20.

Comparative Example 32 (Synthesis of Polyether Polyurethane Prepolymer Having Isocyanate Group at Both Terminals) A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with polypropylene glycol having a number average molecular weight of 2000. Add 85 parts and 15 parts of tolylene diisocyanate, and add 8 in a nitrogen stream.
By stirring for 3 hours at 0 ° C. and reacting, a isocyanate-terminated polyether polyurethane prepolymer [32] for comparison was obtained.

Comparative Example 33 (Synthesis of Polyester Polyurethane Prepolymer Having Isocyanate Group at Both Ends) A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with polyester diol 85 having a number average molecular weight of 2000. Department and TDI
Was added thereto, and the mixture was stirred at 80 ° C. for 3 hours in a nitrogen stream to react with it to obtain a comparative isocyanate-terminated polyester polyurethane prepolymer [33].

-Comparative Examples 34 and 35- (Comparative Example Concerning Resin Composition for Flooring Materials) Comparative Examples 32 and 33
The isocyanate-terminated polyether polyurethane prepolymer [32] and the isocyanate-terminated polyester polyurethane prepolymer [33] obtained in
Each comparative polyurethane composition (resin composition for flooring materials) having the composition shown in Table 1 was produced, and the hardness, surface tackiness, and durability (hydrolysis resistance and heat resistance) of these compositions were measured and evaluated. The results are shown in Table 20.

Example 58- (Synthesis of a Polymer Having a Polymerizable Unsaturated Group at Both Terminals) In Example 40, the polymer [10] was replaced with 137 parts of the polymer.

[9] The same operation as in Example 40 was repeated except that 60 parts of the polymer was used, to obtain a polymer [58].

-Example 59- (Synthesis of a Polymer Having a Polymerizable Unsaturated Group at Both Terminals) In Example 40, 131 parts of the polymer [16] was used instead of 137 parts of the polymer [10]. The same operation as in Example 40 was repeated except that a polymer [59] was obtained.

-Example 60- (Synthesis of Polymer Having Polymerizable Unsaturated Groups at Both Terminals) In Example 40, 462 parts of polymer [19] was used instead of 137 parts of polymer [10]. Other than that, the same operation as in Example 40 was repeated to obtain a polymer [60].

-Example 61- (Synthesis of Polymer Having Polymerizable Unsaturated Groups at Both Terminals) In Example 40, 526 parts of polymer [20] was used instead of 137 parts of polymer [10]. Other than that, the same operation as in Example 40 was repeated to obtain a polymer [61].

-Example 62- 50 parts of the polymer [58] obtained in Example 58, 48.5 parts of styrene, a silane coupling agent (KBM-503,
1.5 parts of Shin-Etsu Chemical Co., Ltd. was mixed to obtain a resin composition. Next, 200 parts of aluminum hydroxide (Hijilite H-320, average particle size 3.5 μm, manufactured by Showa Denko KK) was added to this resin composition and kneaded using a high speed stirrer. Next, 0.8 part of Kayaester O (t-butylperoxy-2-ethylhexanoate, manufactured by Kayaku Nouri Co., Ltd.) as a curing agent was added and mixed, and then defoamed under reduced pressure to prepare a blend. Obtained. The viscosity of this compound is 30 ° C.
It was 4.8 poise.

This composition was poured into a 1000.times.600.times.6 mm casting mold and cured at 60.degree. C., followed by curing in 30 minutes and post-curing at 120.degree. C. for 2 hours.
The obtained cured product was milky white and had a marble tone that scatters light beautifully, had flame retardancy, and was excellent in impact resistance and machinability as shown in Table 21. .

-Examples 63 to 66-Cured products were obtained in the same manner as in Example 62 except that the compounding compositions shown in Table 21 were used. These cured products scattered milky white light, had flame retardancy, and were excellent in impact resistance and machinability as shown in Table 21.

-Comparative Example 36- 27 parts of polymethyl methacrylate (Acrypet MD011, manufactured by Mitsubishi Rayon Co., Ltd.) was replaced with 73 parts of methyl methacrylate.
To obtain a methyl methacrylate syrup (resin solution) having a viscosity of 5 poise. Next, 200 parts of aluminum hydroxide (Hidilite H-320, average particle size 3.5 μm, manufactured by Showa Denko KK) was added to this resin liquid, and the mixture was kneaded using a high speed stirrer. Next, 0.8 part of Kayaester O (manufactured by Kayaku Nouri Co., Ltd.) was added as a curing agent, mixed and then degassed under reduced pressure to obtain a resin formulation for comparison. The viscosity of this resin formulation is 200 poise at a liquid temperature of 30 ° C.,
Casting was difficult because many air bubbles remained and the fluidity was poor. This resin compound is 1000 x 600 x 6 m
It was poured into the m casting mold and cured at 60 ° C.,
It was cured in 20 minutes and post-cured at 110 ° C. for 2 hours.

As for the physical properties of the obtained cured product, as shown in Table 22, there was a problem in impact resistance. -Comparative Example 37-As shown in Table 22, Example 62 was repeated except that 20 parts of ethylene glycol dimethacrylate was used instead of 50 parts of the polymer [58] having a polymerizable unsaturated group at both ends.
The same operation was performed to obtain a cured product.

The physical properties of the obtained cured product are as shown in Table 22, and the impact resistance and workability were poor. -Comparative Example 38- 30 parts of trimethylolpropane trimethacrylate, 50 parts of styrene, 20 parts of methyl methacrylate and a silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)
1.5 parts were mixed to obtain a monomer mixture.

Next, 300 parts of aluminum hydroxide (Hijilite H-320, average particle size: 3.5 μm, manufactured by Showa Denko KK) was added to this mixed solution and kneaded using a high-speed stirrer. Then, Kayaester P-70 as a curing agent
0.5 parts by weight of (t-butyl peroxypivalate, manufactured by Kayaku Nouri Co., Ltd.) was added, mixed and defoamed under reduced pressure to obtain a comparative formulation. The viscosity of this compound is 3
It was 10 poise at 0 ° C.

This formulation is then added to 1000 × 600 × 6.
When poured into a casting mold of mm and cured at 50 ° C,
It was cured in 45 minutes and post-cured at 120 ° C. for 2 hours. The obtained cured product has a milky white, marble-like translucency that scatters light beautifully, and has flame retardancy.
As shown in Table 22, the heat distortion temperature was as high as 230 ° C., but the impact resistance and workability were poor.

Comparative Example 39 Vinyl ester resin (55 parts of bisphenol A type epoxy acrylate resin dissolved in 45 parts of styrene)
Aluminum hydroxide (Hidilite H-320, average particle size 3.5) was added to a resin solution prepared by mixing 1.5 parts of 100 parts of silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.).
200 parts of Micron, manufactured by Showa Denko KK were added and kneaded using a high-speed stirrer. Next, 0.8 part of Kayaester O (manufactured by Kayaku Nouri Co., Ltd.) was added as a curing agent, mixed and then degassed under reduced pressure to obtain a resin formulation for comparison.

The viscosity of this resin composition was 3 at a liquid temperature of 30 ° C.
Since it was 00 poise, many bubbles remained, and the fluidity was poor, which made casting difficult. 1 of this resin blend
When the mixture was poured into a casting mold of 000 × 600 × 6 mm and cured at 60 ° C., it was cured in 50 minutes and further post-cured at 110 ° C. for 2 hours. The physical properties of the obtained cured product are shown in Table 2.
As shown in 2, there were problems in impact resistance and workability.

Example 67 (Synthesis of Polymer Having Carboxyl Group at Both Terminals) The polymer obtained in Example 9 was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer.

[9] 140 parts, maleic anhydride 1
Charged 8.8 parts and 2.8 parts of triethylamine, 80 ° C
After stirring for 6 hours, a polymer [67] was obtained.

With respect to the physical properties of the polymer [67], the number average molecular weight (Mn) was 3,300 as measured by GPC, and the average number of terminal carboxyl groups (Fn (COOH)) was 3.30 by titration with an alcoholic KOH and the above number average molecular weight. It was 9 (mol / polymer 1 mol). From this, it is considered that the reaction proceeded quantitatively. -Example 68- (Synthesis of polymer having carboxyl groups at both ends) 140 parts of the polymer [17] obtained in Example 17 and succinic anhydride were placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. Charge 11.3 parts, sodium acetate part 2.1, 80 ℃
After stirring for 6 hours, a polymer [68] was obtained.

With respect to the physical properties of the polymer [68], the number average molecular weight (Mn) was 4,800 as measured by GPC, and the average number of terminal carboxyl groups (Fn (COOH)) was 3.80 by titration with an alcoholic KOH and the previous number average molecular weight. It was 6 (mol / polymer 1 mol). From this, it is considered that the reaction proceeded quantitatively. -Example 69- (Synthesis of polymer having carboxyl groups at both ends) 165 parts of the polymer [18] obtained in Example 18 and phthalic anhydride were placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. 31 parts and 2.0 parts of triethylamine were charged and stirred at 80 ° C. for 6 hours to obtain a polymer [69].

With respect to the physical properties of the polymer [69], the number average molecular weight (Mn) was 3200 as measured by GPC, and the average number of terminal carboxyl groups (Fn (COOH)) was 3.200 by titration with an alcoholic KOH and the above number average molecular weight. It was 6 (mol / polymer 1 mol). From this, it is considered that the reaction proceeded quantitatively. -Example 70- (Evaluation of epoxy resin composition) The polymer [67] obtained in Example 67 was mixed as a rubber component with an epoxy resin and a curing agent in a ratio shown in Table 23 to obtain an epoxy resin composition. It was

An adhesion test and a heat resistance test were conducted on this epoxy resin composition. The adhesion test, as an adherend,
Thickness 1.5mm (0.5mm for T-type peel test)
The cold-rolled steel sheet of No. 1 was ground with # 100 sandpaper, washed and degreased with acetone, heated at 150 ° C. for 1 hour to cure the adhesive, and the tensile shearing force and T-type peel strength were measured. It was

For the heat resistance test, 12 samples of the adhesion test were used.
It was allowed to stand for about 6 days under hot air drying at 0 ° C., and an adhesion test was performed before and after leaving for hot air drying to determine the strength retention. The results are shown in Table 23. —Example 71— (Evaluation of Epoxy Resin Composition) The same as Example 70 except that the polymer [67] and the epoxy resin were preheated at 150 ° C. for 3 hours and then mixed with a curing agent. The operation was repeated to prepare an epoxy resin composition, and perform an adhesion test and a heat resistance test on the obtained epoxy resin composition. The results are shown in Table 23.

-Examples 72 and 73- (Evaluation of Epoxy Resin Composition) As shown in Table 23, in Example 70, the same amount of the polymers [68] and [69] was used instead of the polymer [67]. Example 7 except using
The same operation as 0 was repeated to prepare an epoxy resin composition, and to perform an adhesion test and a heat resistance test on the obtained epoxy resin composition. The results are shown in Table 23.

-Comparative Example 40- (Evaluation of Comparative Epoxy Resin Composition) As shown in Table 23, in Example 70, the polymer [6
The same operation as in Example 70 was repeated except that [7] was not used, and a comparative epoxy resin composition was prepared and an adhesion test was performed on the obtained comparative epoxy resin composition.

The results are shown in Table 23. -Comparative Example 41- (Evaluation of Comparative Epoxy Resin Composition) As shown in Table 23, in Example 70, the polymer [6
7] instead of Hiker CTBN1300 manufactured by Ube Industries
The same operation as in Example 70 was repeated except that the same amount of X8 was used, and the preparation of the comparative epoxy resin composition and the adhesion test and heat resistance test of the obtained comparative epoxy resin composition were performed. The results are shown in Table 23.

-Comparative Example 42- (Evaluation of Comparative Epoxy Resin Composition) As shown in Table 23, in Example 70, the polymer [6
7] instead of Hiker CTBN1300 manufactured by Ube Industries
With the same amount of X8, this hiker CTBN13
Example 70 except that 00X8 was preheated with epoxy resin at 150 ° C. for 3 hours in advance and then mixed with a curing agent.
The same operation was repeated to prepare a comparative epoxy resin composition, and perform an adhesion test and a heat resistance test on the obtained comparative epoxy resin composition. The results are shown in Table 23.

[0217]

[Table 1]

[0218]

[Table 2]

[0219]

[Table 3]

[0220]

[Table 4]

[0221]

[Table 5]

[0222]

[Table 6]

[0223]

[Table 7]

The annotations in Table 7 above are as follows. * 1: For the polymer [4], it is calculated from the residual ratio of the monomer by gas chromatography after the completion of the polymerization, and for the polymers [5] to [22], the nonvolatile content of the polymerization solution after the completion of the polymerization. Calculated from * 2: Measured by GPC using a standard polystyrene calibration curve. * 3: Ratio of weight average molecular weight (Mw) to number average molecular weight (Mn). * 4: The average number of terminal hydroxyl groups (Fn (OH)) is JIS-
It was calculated based on the OH value determined according to K-1557 and the value of the number average molecular weight measured in * 2 above. * 5: First, the obtained polymer and Sumidule N-75
(Trifunctional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd.), and the molar ratio of isocyanate group to hydroxyl group is 1.
After mixing to 1/1 to make a toluene solution of about 40%, a small amount of dibutyltin dilaurate as a catalyst was added and mixed well with stirring, and the mixture was reacted at 80 ° C. for 3 hours to give a polyurethane film. Obtained.

Next, after sufficiently drying the film,
8 for Soxhlet extraction using tetrahydrofuran as a solvent
The weight percentage of the insoluble matter remaining without extraction over time was expressed as the gel fraction. * 6: First, the obtained polymer and desmodul H (2
Functional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd., and the molar ratio of isocyanate group to hydroxyl group is 1.0.
After mixing 5/1 to make a toluene solution of about 40%, a small amount of dibutyltin dilaurate as a catalyst was added, and the mixture was stirred well and allowed to react at 80 ° C. for 3 hours to give a polyurethane film. Obtained. Next, after the film was sufficiently dried, it was subjected to Soxhlet extraction using tetrahydrofuran as a solvent for 8 hours, and the weight% of the insoluble matter remaining without being extracted was expressed as a gel fraction.

[0226]

[Table 8]

[0227]

[Table 9]

[0228]

[Table 10]

[0229]

[Table 11]

[0230]

[Table 12]

[0231]

[Table 13]

[0232]

[Table 14]

[0233]

[Table 15]

[0234]

[Table 16]

[0235]

[Table 17]

[0236]

[Table 18]

[0237]

[Table 19]

[0238]

[Table 20]

[0239]

[Table 21]

[0240]

[Table 22]

[0241]

[Table 23]

[0242]

According to the production method of the present invention, a wide range of vinyl-based monomers including polar vinyl-based monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester can be used at both ends. A polymer having a hydroxyl group (polymer A) can be obtained easily, inexpensively and efficiently.

The polymer A obtained by this production method is
By having hydroxyl groups at both ends, it can be used as a raw material or additive for various resins such as polyester resin, polyurethane resin, polycarbonate resin, and various block polymers, or as a polymer (paint, high solid, low temperature curing). Etc.), elastic wall material, waterproof film, adhesive, floor material, tackifier, adhesive, binder (magnetic recording medium, ink binder, casting binder, baked brick binder, graft material, microcapsule, glass fiber) Sizing, etc.), sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV
・ EB curable resin, thermosetting elastomer, thermoplastic elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coating agent, artificial marble resin, artificial marble impact resistance Agent, ink resin, film (laminate adhesive, protective film, etc.),
It is very useful for applications such as laminated glass resins, reactive diluents, various molding materials, elastic fibers, artificial leather, synthetic leather, dispersants, aqueous urethane emulsions, and reacts hydroxyl groups at both ends by a suitable method. By letting
Functional group other than hydroxyl group (for example, polymerizable unsaturated group such as vinyl group, formyl group, amino group, carboxyl group, ethynyl group, epoxy group, silanol group, alkoxysilyl group, hydrosilyl group, mercapto group, oxazoline group,
Maleimide group, azlactone group, lactone group, bromine, chlorine, etc.) can be easily converted into a polymer having both ends. This polymer is also very useful. For example,
Polymer having carboxyl groups at both ends (Polymer C)
Is very effective as an impact resistance imparting agent for epoxy adhesives. Further, by adding a plurality of ethylene oxide or propylene oxide to the terminal hydroxyl group of the polymer A, a surfactant, urethane foam, cement water reducing agent,
It becomes a raw material for compatibilizers.

A composition containing as an essential component a polymer A obtained by the production method of the present invention and a polyfunctional compound (f) having two or more functional groups capable of reacting with a hydroxyl group in one molecule (composition A ) Is various resins such as polyester resin, polyurethane resin and polycarbonate resin, various block polymers, paints (high solid, low temperature curing, etc.), elastic wall materials, waterproof coating materials, adhesives, flooring materials, tackifiers, Adhesives, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), sealing materials, urethane foam (hard, semi-hard, soft), urethane RIM, UV EB curable resin, thermosetting elastomer, thermoplastic elastomer, microcellular, fiber processing agent, plastic , Sound absorbing material, vibration damping material, surfactant, gel coating agent, artificial marble resin, artificial marble impact resistance imparting agent, ink resin, film (laminate adhesive, protective film, etc.), laminated glass resin, reaction Flexible and tough mechanical properties when used as a raw material for functional diluents, various molding materials, elastic fibers, artificial leather, synthetic leather, dispersants, aqueous urethane emulsions, and various resin additives and their raw materials. In addition to the above, depending on the type of the monomer component (a) constituting the main chain of the polymer A, very good transparency, weather resistance, water resistance, hydrolysis resistance, chemical resistance, etc. The physical properties are also fully exhibited, and very good physical properties are shown.

For example, as the polymer A, a low molecular weight polymer having a weight average molecular weight of about 1000 to 10000 is used, and this is combined with a bifunctional isocyanate compound and the like, and after application to a substrate, chain extension and adhesion are performed. When used as an agent, when a conventional polymer obtained by copolymerizing a vinyl-based monomer having a functional group is used (usually, one having a weight average molecular weight of 100,000 or more is used)
Compared with the above, the viscosity of the pressure-sensitive adhesive composition is low, so that the amount of solvent used can be reduced and the workability is improved. A composition is obtained.

When the composition A is used for an adhesive composition, the composition A is used as one of the essential components.
Therefore, when the same adhesive performance is obtained as compared with the case of using an acrylic polymer obtained by copolymerizing a vinyl-based monomer having a functional group, the viscosity of the adhesive composition Is low, and therefore the amount of solvent used can be reduced, workability can be improved, and other effects not obtained with conventional adhesive compositions can be obtained. Further, the adhesive using the composition A is superior in heat resistance to the adhesive using the polyether polyol currently used, and is also compared to the adhesive using the polyester polyol currently used. And has excellent hydrolysis resistance.

When the composition A is used for urethane foam, since the polymer A is used in combination with a conventionally known isocyanate compound, the flexibility, weather resistance, heat resistance, water resistance, chemical resistance and impact resilience are obtained. In, it is possible to obtain an effect that the conventional urethane foam composition does not have. Further, the urethane foam using the composition A is superior in heat resistance to the urethane foam using the polyether polyol which is currently used, and compared with the urethane foam using the polyester polyol which is currently used. Excellent resistance to hydrolysis.

When the composition A is used for a sealing material, by combining the polymer A with a conventionally known isocyanate compound or the like, it is flexible and tough, and has weather resistance, heat resistance, water resistance, chemical resistance and impact resilience. In terms of the rate, an effect not obtained by the conventional sealant composition can be obtained. Also,
The sealing material using the composition A is superior in heat resistance to the sealing material using the polyether polyol which is currently used.

Both ends obtained by reacting the polymer A with a compound (j) having two reactive groups of a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group in one molecule. In addition to the polymer having a polymerizable unsaturated group (polymer B),
When a composition containing a vinyl-based monomer having at least one polymerizable unsaturated group in one molecule as an essential component is used for a gel coat resin composition, a resin composition for artificial marble, a resin composition for laminated glass, etc. , The reaction shrinkage during molding is small,
It is possible to obtain a resin having a low viscosity during work, good workability, a large hardness of a cured product, toughness, and good weather resistance.

The artificial marble obtained from the above-mentioned resin composition for artificial marble is excellent in heat resistance and weather resistance, and by using the polymer B, the composition has a small shrinkage due to polymerization during molding. Problems such as cracks occurring during molding are solved. Further, since it is incorporated into the crosslinked structure at the terminal of the polymer, by using a rubber component in the polymer main chain, the flexibility of the molded product is greatly improved, and a molded product with extremely good impact resistance is obtained. You can Also, for the same reason, there is no chipping during cutting and the machinability is good.

Further, in order to suppress the polymerization shrinkage at the time of polymerization and impart flexibility to the molded product, unlike the conventional case where a thermoplastic polymer having no polymerizable unsaturated group is added, the addition is performed. Since the polymer has a polymerizable unsaturated group at both ends, it is incorporated into the crosslinked structure even after molding, so even if the amount added is increased, problems such as reduced heat resistance do not occur, and flexibility is also high. Is also given enough.

Polyurethane obtained by reacting polymer A with polyfunctional isocyanate compound (g), and
The polyester obtained by reacting the polymer A with the compound (i) having two or more carboxyl groups in one molecule, when used as a molding material, not only has flexible and tough mechanical properties, but also has a heavy weight. Depending on the type of the vinyl-based monomer component (a) constituting the main chain of the united product A, it also has very good physical properties such as transparency, weather resistance, water resistance, hydrolysis resistance, oil resistance, and chemical resistance. It is a very useful material that shows its fullness and shows very good physical properties.

It is obtained by reacting the polymer A with a compound (k) and / or an acid anhydride having two reactive groups, a functional group capable of reacting with a hydroxyl group and a carboxyl group, in one molecule. The polymer having a carboxyl group at both ends (Polymer C) is the same as the polymer A having a hydroxyl group by arbitrarily selecting the type of the vinyl-based monomer (a) constituting the main chain, It has transparency, weather resistance, water resistance, hydrolysis resistance, chemical resistance, and various resins such as polyester derived from the polymer C are very stretchable (have good bending workability) and Since it exhibits the property of being tough, paints, adhesives, various molding materials, resin modifiers (impact resistance imparting materials), damping materials, elastic wall materials, floor materials,
It is useful as a raw material for fiber processing materials, UV / EB curing resins, and the like. Further, this polymer C has a feature that it can be used as a curing agent and an additive for an epoxy resin which has been difficult to use at the terminal of a hydroxyl group.

Next, the polymer C and the compound (l) having two or more functional groups capable of reacting with the carboxyl group in one molecule.
The resin composition characterized by containing and as an essential component contains the polymer A as an essential component by arbitrarily selecting the type of the vinyl-based monomer (a) constituting the main chain. Similar to composition A, it has transparency, weather resistance, water resistance, hydrolysis resistance, chemical resistance, and various resins such as polyester derived from the composition containing polymer C are very Since it exhibits the characteristics of being stretchable (having good bending workability) and being tough, it can be used in paints, adhesives,
It is useful as a raw material for various molding materials, resin modifiers (impact resistance imparting materials), vibration damping materials, elastic wall materials, floor materials, fiber processing materials, UV / EB curing resins and the like. Further, the composition containing the polymer C is characterized in that it can be used for an epoxy resin composition which has been difficult to use at a hydroxyl group terminal.

In the epoxy resin composition characterized by containing the polymer C as an essential component, addition of the polymer C as a rubber component to the epoxy resin improves the toughness, and at the same time, it has been improved in heat resistance and weather resistance. The effect which was not obtained in the epoxy resin composition of 1) is obtained. That is, polymer C
The epoxy resin composition using is excellent in heat resistance and weather resistance as compared with the epoxy resin compositions in which polybutadiene polyol and polybutadiene / acrylonitrile polyol which are currently used are added.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Ikeuchi 5-8 Nishimitabicho Suita City, Osaka Prefecture Central Research Laboratory of Nippon Shokubai Co., Ltd. (72) Fumihide Tamura 5-8 Nishimitabicho Suita City, Osaka Prefecture Central Research Institute of Nippon Shokubai Co., Ltd.

Claims (2)

[Claims] 1. A method of polymerizing a vinyl-based monomer (a) in the presence of an alcohol (b) using an initiator system (c) essentially comprising an organic peroxide, the method comprising: The non-phosphorus inorganic acid (d) is used, and the above-mentioned four (a),
A method for producing a polymer, characterized in that components other than (b), (c) and (d) are not substantially used. 2. A surfactant (x) as a component other than the vinyl-based monomer (a), the alcohol (b), the initiator system (c), and the non-phosphorus-based inorganic acid (d), and the total amount of the components. Against 10
The method for producing a polymer according to claim 1, wherein the amount is less than wt%.