JP2002003604A - Resin modifier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin modifier which gives flexibility to resins to be modified and which has less odor and causes less deterioration of mechanical properties such as flexural strength or adhesive strength. SOLUTION: The resin modifier has a specific structure having one or more terminal hydroxyl or mercapto groups as shown in formula 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin modifier. More specifically, the present invention relates to a resin modifier comprising a novel compound that improves the flexibility and adhesion of a resin.

[0002]

2. Description of the Related Art Conventionally, as a method for improving the flexibility of a resin, a predetermined amount of polysulfide or the like is added to a monomer and / or oligomer before a curing reaction for forming a resin, and an isocyanate group is added in the presence of a tertiary amine catalyst. It is known to introduce a polysulfide skeleton into a resin skeleton by adding a thiol group to an epoxy group or a vinyl group.

[Problems to be solved by the invention]

[0003] However, while this method can provide flexibility, it has a problem that mechanical properties such as bending strength and adhesive strength are deteriorated, and polysulfide has a problem that it is difficult to perform a work with a strong odor. I was

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, the present invention is a resin modifier comprising the compound (A) represented by the following general formula (1).

[0005]

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Wherein X ¹ , X ² and X ³ are each independently an oxygen or sulfur atom; Y ¹ is —NR ^3- (R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms), an oxygen atom and At least one divalent structure selected from the group consisting of sulfur atoms;
Y ^2, Y ³ is a direct bond or -NR ³ - (R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms), at least one divalent structure selected from the group consisting of an oxygen atom and a sulfur atom; Z ¹ Is hydrogen, —NHR ³ (R ³ is hydrogen or an alkyl group having 1 to 3 carbon atoms), at least one monovalent structure selected from the group consisting of a hydroxyl group and a mercapto group; R ¹ is an ether having 2 to 28 carbon atoms A straight-chain or branched hydrocarbon group which may contain a bond; R ₂ is a direct bond or 1 having a molecular weight of 14 to 20,000;
AO is a group in which an alkylene (2-4 carbon) oxide is ring-opened; k and l are each independently 0 or 1
M and n each represent a valence, m is an integer of 1 to 8, n is 0 or an integer of 1 to 7, and m + n is 1 to 8
Represents the integer of

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, compound (A) is
It is represented by the general formula (1). Where X¹, X^TwoAnd X^Three
Is each independently an oxygen or sulfur atom, preferably
X₁And Z₁Is a sulfur atom and Y₁Is an oxygen atom. ; Y¹
Is -NR^Three− (R^ThreeIs hydrogen or alkyl having 1 to 3 carbon atoms
Group), an oxygen atom and a sulfur atom
It is at least one kind of divalent structure. Preferably at -NH-
is there. Z¹Is hydrogen, -NHR^Three(R ^ThreeIs hydrogen or carbon number 1
Consisting of a hydroxyl group and a mercapto group)
At least one monovalent structure selected from the group
Or -NH_TwoIt is. R¹Is an ether having 2 to 28 carbon atoms
A linear or branched hydrocarbon group which may contain a bond
And the linear hydrocarbon group is a divalent hydrocarbon group —CH
_Two(CH_Two)_mA group represented by-(m is an integer of 1 to 9) (eg,
For example, -CH_TwoCH_Two-, -CH_TwoCH_TwoCH_Two-, -CH_Two
CH_TwoCH_TwoCH_TwoCH_Two-Etc.); trivalent hydrocarbon groups, for example
BA> CH (CH_Two)_m-(M is an integer of 1 to 9)
Group (eg,> CHCH_Two-,> CHCH_TwoCH_Two-,>
CHCH_TwoCH_TwoCH_Two-,> CHCH_TwoCH_TwoCH_TwoCH_Two
CH_Two-Etc.); a tetravalent hydrocarbon group such as> CH (C
H_Two)_mA group represented by CH <(m is an integer of 0 to 8) (eg,
For example,> CHCH <,> CHCH_TwoCH <,> CHCH_TwoC
H_TwoCH <,> CHCH_TwoCH_TwoCH_TwoCH_TwoCH <etc.)
And preferably a trivalent hydrocarbon group.
Preferably> CHCH_Two-. This branch
Is a straight chain which may contain an ether bond having 1 to 18 carbon atoms.
Chain or branched hydrocarbon group such as methyl group,
Group, propyl group, butyl group, hexyl group, 2-ethyl
Hexyl, octyl, decyl, dodecyl, milli
Stillyl, stearyl, butyloxymethyl, 2-
Ethylhexyloxymethyl group, phenoxy group, lauri
And a luoxymethyl group. R¹Has 1 carbon atom
If there is, the odor becomes severe and work becomes difficult, and carbon
If the number exceeds 28, the compatibility with the resin to be modified lowers.

R ₂ is a direct bond or a number average molecular weight of 14 to 2
Represents a 000- to 8-valent organic group. Number average molecular weight 1
The organic group of 4 to 20,000 represents a residue obtained by removing active hydrogen and atoms (N, O, S) to which active hydrogen is bonded from the active hydrogen-containing compound (F) described later. Preferably the molecular weight is 28-5,000, particularly preferably 28-5,000.
500. When the molecular weight of the organic group exceeds 20,000, the compatibility with the resin to be modified decreases. AO represents a group in which an alkylene (C2-4) oxide is opened. As the alkylene oxide, a hydrocarbon oxide having 2 to 25 carbon atoms (referred to as AO) such as ethylene oxide (EO), propylene oxide (PO), 1,2-,
Examples thereof include 2,3- or 1,3-butylene oxide, tetrahydrofuran (THF), styrene oxide, α-olefin oxide, epichlorohydrin and the like. AO may be used alone or in combination of two or more kinds. In the latter case, a block addition (chip type, balance type, active secondary type, etc.) or a random addition or a mixed system of both (a chip added after random addition: in the molecule) 0 to 50% by weight (preferably 5%)
-40% by weight) and 0-30% by weight (preferably 5
25% by weight) EO chain chipped at the molecular end]
May be. Among these AOs, preferred is EO
Alone, PO alone, THF alone, combined use of PO and EO,
A combination of PO and / or EO with THF (in the case of combined use, random, block, or a mixture of both). k and l are each independently 0 or an integer of 1 to 200, preferably 0 to 50. When k and l exceed 200, the water resistance decreases. m and n represent valences, m is an integer of 1 to 8, n
Is 0 or an integer of 1 to 7, and m + n represents an integer of 1 to 8. When m + n is 0, the elution from the resin to be modified is fast and the modifying effect is not sustained, and m is an integer of 9 or more or n is 8
If the above integer or m + n is 9 or more, the compatibility with the resin to be modified decreases.

The method for producing the compound (A) of the present invention is not particularly limited, but is preferably from 0.8 to 1.0 based on a cyclic carbonate compound, for example, a cyclic dithiocarbonate compound described in detail in JP-A-5-247027. It is obtained by reacting a compound containing twice equivalent of active hydrogen. Examples of the cyclic carbonate compound include a cyclic thiocarbonate compound, a cyclic dithiocarbonate compound, a cyclic trithiocarbonate compound and the like, and a cyclic dithiocarbonate compound is preferable. The structure of the cyclic carbonate compound is represented by the general formula (2).

[0010]

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Wherein X ¹ , X ² , X ³ and R ¹ are the same as those described in formula (1). This cyclic carbonate compound is obtained by reacting carbon disulfide or carbonyl sulfide with monoepoxide. Is obtained. The reaction may be the same as that described in detail in Japanese Patent Application No. 11-32229. As the cyclic carbonate compound, specifically, 1,3-oxothiolan-2-thione, 5-methyl-1,3-oxothiolan-2-thione, 5-ethyl-1, as a reactant of carbon disulfide and monoepoxide. 3-oxothiolan-2-thione, 5-phenyl-1, 3-oxothiolan-2-thione, 5-butyloxymethyl-1,
3-oxothiolan-2-thione, 5-allyloxymethyl-1, 3-oxothiolan-2-thione, 5- (2
-Ethylhexyl) oxymethyl-1,3-oxothiolan-2-thione, 5-phenoxy-1,3-oxothiolan-2-thione, 5-lauryloxymethyl-1,
3-oxothiolan-2-thione and the like; 1,3-oxolan-2-thione, 5-methyl-1,3-oxolan-2- as a reaction product of carbonyl sulfide and monoepoxide
Thione, 5-phenyl-1,3-oxolan-2-thione, 5-butyloxymethyl-1,3-oxolan-2
-Thion, 5-allyloxymethyl-1,3-oxolan-2-thione, 5- (2-ethylhexyl) oxymethyl-1,3-oxolan-2-thione, 5-phenoxy-1,3-oxolan-2 -Thione, 5-lauryloxymethyl-1, 3-oxolane-2-thione and the like. Of these, preferably 5-alkyl-1,
1,3-oxothiolane-2-thione, 5-alkoxymethyl-1,3-oxothiolane-2-thione, etc.
It is an oxothiolan-2-thione derivative, particularly preferably 5-alkoxymethyl-1,3-oxothiolan-2-thione. Examples of the compound containing active hydrogen that reacts with the cyclic dithiocarbonate compound include those represented by the following general formula (3).

[0012]

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[Wherein, Y ¹ , Y ² , Y ³ , (AO), R ²
, Z ¹ , k, l, m, and n are the same as those described in Formula (1).] Here, the compound represented by Formula (3) is (HY ² ) m
Alkylene oxide (AO) is added to -R ^2- (Y ³ H) n
化合物 200 mol, and Z ¹ is H. R ² is directly bonded or has a molecular weight of 12 to
It is a 20,000-valent organic group of 20,000, and represents a residue obtained by removing active hydrogen and atoms (N, O, S) to which active hydrogen is bonded from an active hydrogen-containing compound (F) described later.

As the active hydrogen-containing compound (F), ammonia, amines (F1) having a molecular weight of 17 to 20,000,
Examples thereof include alcohols (F2) and thiols (F3). The amines (F1) include the following. (F1-1) Aliphatic amines (C1-18,
(I) a functional primary group or a secondary monoamine (having a carbon number of 1 to 1);
8) [methylamine, dimethylamine, n-butylamine, di-n-butylamine, 2-ethylhexylamine, n-laurylamine, stearylamine, etc.]; (ii) aliphatic polyamine {alkylene diamine having 2 to 6 carbon atoms; Ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-6)
Polyamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; (iii) alkyl (1 to 4 carbon atoms) or hydroxyalkyl (carbon Formulas 2 to 4) Substituted [dialkyl (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine,
2,5-dimethyl-2,5-hexamethylenediamine,
(Iv) alicyclic or heterocyclic-containing aliphatic polyamines [3,9-
Bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like]; (v) aromatic ring-containing aliphatic amines (8 to 15 carbon atoms) (xylylenediamine, Tetrachloro-p-xylylenediamine, etc.);

(F1-2) alicyclic polyamine (having 4 to 4 carbon atoms)
15, functional groups 2-3): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4
'-Methylenedicyclohexanediamine (hydrogenated methylenedianiline) and the like; (F1-3) heterocyclic polyamine (4 to 15 carbon atoms, 2 to 3 functional groups): piperazine, N-aminoethylpiperazine, 1,4- (F1-4) polyamide polyamine: dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) of polyamine; (F1-4) polyamide polyamine: diaminoethylpiperazine, 1,4 bis (2-amino-2-methylpropyl) piperazine, etc. (The above alkylenediamine having 2 to 7 functional groups,
Polyamide polyamine (number average molecular weight 200 to 100) obtained by condensation with polyalkylene polyamine
(F1-5) polyetheramine: hydride of cyanoethylated polyether mono- or polyol or modified terminal amination (number of functional groups 1 to 8, molecular weight 50 to 10,000)
0), and examples thereof include an alkylene oxide adduct of an alcohol having a hydroxyl group, a hydroxyl group reductive amination at the terminal of an alkylene oxide polymer, and a hydride of an acrylonitrile adduct to those terminal hydroxyl groups. The alcohol having a hydroxyl group has 1 to 1 carbon atoms.
And hydrocarbon alcohols which may have 12 ether groups. Specifically, monohydric alcohols such as methanol, ethanol, n-butanol, and 2-ethylhexyl alcohol; ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4'-hydroxycyclohexyl) propane, etc. Trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, 4 ® sugar and the like
And octahydric alcohols.

As the alkylene oxide (AO), the same as those described above can be used. AO alone 2
More than one species may be used in combination, and in the latter case, a block addition (chip type, balance type, active secondary type, etc.) or a random addition or a mixed system of both (chiped after random addition: arbitrarily distributed in the molecule) Having 0 to 50% by weight (preferably 5 to 40% by weight) of ethylene oxide chains;
0 to 30% by weight (preferably 5 to 25% by weight) of an EO chain chipped at the molecular end]. These A
Of O, preferred are EO alone, PO alone, THF
Alone, a combination of PO and EO, PO and / or EO and T
HF is used in combination (in the case of combined use, random, block, and a mixed system of both). (F1-6) Epoxy-added polyamine: epoxy compound (for example, ethylene oxide, propylene oxide,
Monoepoxides such as phenylglycidyl ether)
An epoxy-added polyamine (having a molecular weight of 1) obtained by adding 1 to 30 moles of 1 mole to a polyamine (the above-described alkylene diamine, polyalkylene polyamine, etc.).
00 to 1000) and the like;

(F1-7) cyanoethylated polyamine: a cyanoethylated polyamine obtained by an addition reaction of acrylonitrile with a polyamine (the above-mentioned alkylenediamine, polyalkylenepolyamine and the like), (biscyanoethyldiethylenetriamine and the like) (molecular weight 100 to 500)
(F1-8) Other polyamine compounds: (i) hydrazines (hydrazine, monoalkylhydrazine, etc.); (ii) dihydrazides (succinic dihydrazide, adipic dihydrazide, isophthalic dihydrazide,
(Iii) guanidines (butylguanidine, 1-cyanoguanidine, etc.); (iv) dicyandiamide, etc .; and a mixture of two or more thereof. Of the above (F1-1) to (F1-8), (F1-
5). The alcohols (F2) include the following. The compound is not particularly limited as long as it has a hydroxyl group in the molecule, but is a mono- to octavalent alcohol (F2-1), a polyalkylene ether mono- or polyol (F2-2), a polyester mono- or polyol (F2-3), a polymer polyol (F2-4), polybutadiene polyol (F2-
5) Castor oil-based polyols (F2-6), acrylic polyols (F2-7) and mixtures of two or more of these. Examples of the monovalent to octavalent alcohol (F2-1) include the same ones as those described in (F1-5).

As the polyalkylene ether mono- or polyol (F2-2), an active hydrogen-containing polyfunctional compound (a) having 1 to 8 functional groups can be added to an alkylene oxide (hereinafter referred to as AO).
) And mixtures of two or more of these compounds. The number average molecular weight of the polyalkylene ether mono- or polyol (F2-2) is usually 75
２０20,000, preferably 50〜１０10,000, more preferably 1,000〜3,000. Examples of the active hydrogen atom-containing compound (a) include alcohol (a1), phenols (a2), amines (a3), carboxylic acid (a4),
Phosphoric acids (a5), thiols (a6) and the like; Alcohol (a1); the same as the above (F2-1). As the phenols (a2), there are 6 to 15 carbon atoms;
Examples thereof include phenols having 1 to 3 functional groups, for example, phenols such as phenol, pyrogallol, catechol and hydroquinone, as well as bisphenols such as bisphenol A, bisphenol F and bisphenol S.

The amines (a3) include those described in the above (F1-1)
(I) an aliphatic primary or secondary monoamine; an ethylene diamine, trimethylene diamine, hexamethylene diamine, diethylene triamine or the like having 2 to 8 or more carbon atoms having 2 to 8 or more aliphatic polyamines; piperazine, N-aminoethylpiperazine and other heterocyclic polyamines described in JP-B-55-21044; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine , Diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine and other aromatic polyamines; and mono-, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc. - or tri - alkanol (having 2 to 4 carbon atoms) amine, etc. can be mentioned. The polycarboxylic acid (a4) has 2 to 10 carbon atoms and 1 to 3 functional groups.
Carboxylic acids such as acetic acid and propionic acid; aliphatic polycarboxylic acids such as succinic acid and adipic acid; and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid.

The phosphoric acids (a5) include phosphoric acid, phosphonic acid and the like. Examples of the thiol (a6) include a thiol obtained by reacting the glycidyl group-containing compound with hydrogen sulfide. The active hydrogen-containing polyfunctional compound (a) described above may be used in combination of two or more. The AO to be added to the active hydrogen atom-containing compound (a) includes the above-mentioned (F)
The same as those described in 1-5) can be mentioned. AO may be used alone or in combination of two or more kinds. In the latter case, a block addition (chip type, balance type, active secondary type, etc.) or a random addition or a mixed system of both (a chip added after random addition: in the molecule) Having 0 to 50% by weight (preferably 5 to 40% by weight) of ethylene oxide chains arbitrarily distributed, and having EO chains of 0 to 30% by weight (preferably 5 to 25% by weight) chipped at molecular ends ]. Of these AOs, preferred are EO alone, P
O alone, THF alone, combined use of PO and EO, and combined use of PO and / or EO with THF (in the case of combined use, random, block, or a mixture of both). The (F2-
The functionality of 2) is usually 1 to 8, preferably 2 to 3, and particularly preferably 2. Polyester polyol (F-
3) includes a low molecular weight diol and / or a polyalkylene ether diol having a molecular weight of 1000 or less and a condensed polyester diol obtained by reacting a dicarboxylic acid, a polylactone diol obtained by ring-opening polymerization of a lactone,
Polycarbonate diols obtained by reacting a low molecular diol with a carbonic acid diester of a lower alcohol (such as methanol) are included.

Examples of the low molecular diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-, 1,3-butanediol, neopentyl glycol and 1,6-hexanediol; Molecular diols [for example, those described in JP-B-45-1474: bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, EO adducts of bisphenol A, etc.], and mixtures of two or more of these. . Examples of the polyalkylene ether diol having a molecular weight of 1,000 or less include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, and a mixture of two or more thereof. Examples of the dicarboxylic acids include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), and ester-forming derivatives of these dicarboxylic acids. [Anhydrides, lower alkyl (1-4 carbon atoms) esters and the like] and mixtures of two or more thereof; examples of lactones include ε-caprolactone, γ-butyrolactone, γ-valerolactone, and two kinds thereof. A mixture of the above is mentioned.

These polyester polyols (F2-
Specific examples of 3) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, and polybutylene azele And polyesterdiols such as polybutylene sebacate diol, polylactone diols such as polycaprolactone diol or triol, and polycarbonate diols such as polyhexamethylene carbonate diol. Polymer polyol (F2-
As 4), in a polyol (the polyalkylene ether polyol and / or the polyester polyol), a radical polymerizable monomer [for example, styrene, (meth) acrylonitrile, (meth) acrylate,
Vinyl chloride and a mixture of two or more of these), and the polymer is finely dispersed. After the completion of the polymerization reaction, the resulting polymer polyol can be used for the production of polyurethane without any post-treatment, but after the completion of the reaction, an organic solvent, decomposition products of a polymerization initiator, unreacted monomers, etc. Is preferably removed by conventional means.

The polymer polyol (F2-
4) is usually 30 to 70%, preferably 40 to 60%,
More preferably 45-55%, most preferably 50-5%.
It is a translucent to opaque white or tan dispersion in which 5% of the total polymerized monomer, ie, polymer, is dispersed in the polyol. Polybutadiene polyol (F2-
5) includes those having a 1,2-vinyl structure,
Examples include those having a 2-vinyl structure and a 1,4-trans structure, and those having a 1,4-trans structure. The ratio between the 1,2-vinyl structure and the 1,4-trans structure can be variously changed, for example, 100:
0 to 0: 100. Polybutadiene glycol (F2-5) includes homopolymers and copolymers (styrene butadiene copolymer, acrylonitrile butadiene copolymer, etc.) and hydrogenated products thereof (hydrogenation rate: for example, 20 to 100%). The number average molecular weight of the polybutadiene glycol (F2-5) is usually from 500 to 10,000. The castor oil-based polyol (F2-6) includes castor oil and modified castor oil (such as castor oil modified with a polyhydric alcohol such as trimethylolpropane and pentaerythritol). Equivalent of polyol (F2) (molecular weight per hydroxyl group)
Is usually 100 to 10,000, preferably 250 to
It is 5,000, more preferably 500-1,500.

Thiol (F3); an alkylthiol compound having 1 to 20 carbon atoms and 1 or more functional groups, for example, 1,4-
Butanedithiol, 1,8-octadienedithiol and the like. Thiols obtained by the reaction of polyepoxide (B1) with hydrogen sulfide; mercaptocarboxylic acids having 2 to 20 carbon atoms and 1 or more mercapto groups (mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptohexanoic acid, mercaptooctanoic acid , Mercaptostearic acid, etc.) and polyol (F). Among them, the compound (F) having active hydrogen is preferably an amine (F1),
Particularly preferred is polyetheramine (F1-5).

If necessary, the above-mentioned alkylene oxide can be added to (F) to give a compound of the general formula (3). The conditions for adding the alkylene oxide may be the same as those described above. Further, the compound of the present invention (A) is obtained by reacting the compound of the general formula (3) with the cyclic polycarbonate compound. At the time of the reaction, a solvent may or may not be used, but any solvent can be used as long as it does not hinder the reaction and dissolves the raw materials and products. Usually, an aprotic solvent is used. For example,
Ethers (tetrahydrofuran, dioxane, diethyl cellosolve, dioxolan, trioxane, dibutyl cellosolve, diethyl carbitol, dibutyl carbitol, etc.), ketones (acetone, methyl ethyl ketone,
Methyl isobutyl ketone, diethyl ketone, etc.), esters (methyl acetate, ethyl acetate, n-butyl acetate, etc.),
Other polar solvents (acetonitrile, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.)
And the like, preferably, tetrahydrofuran, acetone, ethyl acetate and the like. The reaction temperature is usually from 0 to 1
00 ° C, preferably 20 to 50 ° C. The reaction time is 1 minute to 10 hours, preferably 5 minutes to 2 hours. The progress of the reaction can be determined by the consumption of the raw materials used, and can be measured by, for example, a gas chromatograph. The end point of the reaction is the point at which the raw materials used are exhausted.

The compound (A) of the present invention thus obtained has a number average molecular weight of 100 to 30,000,
It is preferably from 00 to 2,000. The number average molecular weight can be measured by a gel permeation (GPC) method. As an example of the measurement conditions, a TSKgel column (super H4000 + H3000 + H200 manufactured by Tosoh Corporation) is used.
0), GPC-8120 (manufactured by Tosoh Corporation) is used.
The viscosity of (A) at 25 ° C. is from 500 to 100,000 cP, preferably from 100 to 20,000 cP.

The resin to which the modifier of the present invention is applied is not particularly limited, and examples thereof include a thermoplastic resin and a thermosetting resin. The following are mentioned as a thermoplastic resin. Addition polymerization system: polyethylene, polypropylene, polystyrene, poly-p-xylylene, polyacrylate, polymethacrylate, polyvinyl chloride, polyvinylidene chloride,
Polyvinyl acetate, fluororesin, polyacrylonitrile,
Diene polymers such as polyvinyl ether and polybutadiene; polycondensation system: polyamide, thermoplastic polyester, polycarbonate, polyphenylene oxide, polysulfone, etc .; polyaddition system: thermoplastic polyurethane, etc .; ring-opening polymerization system: ethylene oxide, propylene oxide,
Alkylene oxide polymers such as tetrahydrofuran, polyacetal, etc .; Examples of the thermosetting resin include the following. Phenolic resin, furan resin, xylene / formaldehyde resin, ketone / formaldehyde resin,
Urea resin, melamine resin, aniline resin, alkyd resin, acrylic resin, unsaturated polyester resin, epoxy resin, triallyl cyanurate resin, polyurethane resin, and the like; among these, thermosetting resins are preferable, and epoxy is particularly preferable. Resin, urethane resin and acrylic resin. This modifier has active hydrogen at the terminal,
Since the active hydrogen reacts with the thermosetting resin, the active hydrogen is firmly incorporated into the resin, so that the active hydrogen stays in the resin without bleeding out for a long period of time, and the modifying function can be held semipermanently.

The method of adding the present modifier is not particularly limited as long as the resin to be modified and the present modifier can be kneaded. For example, in the case of an epoxy resin, an amine-based curing agent and (A) are previously added and kneaded, and the mixture and the epoxy resin are mixed and cured to obtain a cured resin in which the modifier is uniformly dissolved or dispersed. . The kneading device is not particularly limited, such as an extruder, a Banbury mixer, a roller, and a kneader. The amount of the modifier added to the resin to be modified is 100
0.1-20% by weight, preferably 0.5
-15%, more preferably 1-10%. 0.1%
If it is above, the modification effect by addition can be obtained,
When the content is 20% or less, the modifying effect is sufficient, and there is no decrease in physical properties such as strength originally possessed by the resin to be modified. The modifying effects of the present modifier include toughness, flexibility, adhesiveness, etc., and the resin HLB value can be changed by changing the structure of (A). It can also impart the ability to remove substances.

The modifier of the present invention may contain, if necessary, (1) an antioxidant such as a hindered amine, hydroquinone, a hindered phenol, or a sulfur-containing compound; (2) a benzophenone, a benzotriazole, or a salicylic acid. UV absorbers such as esters and metal complexes, (3) Stabilizers such as metal soaps, inorganic and organic salts of heavy metals (eg, zinc, tin, lead, cadmium, etc.), and organic tin compounds, (4) phthalic acid Esters, phosphate esters, fatty acid esters, epoxidized soybean oil, castor oil, plasticizers such as liquid paraffin alkyl polycyclic aromatic hydrocarbons, (5) paraffin wax, microcrystalline wax, polymerized wax, beeswax,
Waxes such as whale wax, low molecular weight polyolefin, (6)
Non-reactive diluents such as benzyl alcohol, tar, and bitumen; (7) reactive diluents such as low-molecular aliphatic glycidyl ether and aromatic monoglycidyl ether; (8) calcium carbonate, kaolin, talc, mica, bentonite, Clay, sericite, asbestos, glass fiber powder,
Carbon fiber powder, aramid fiber powder, nylon fiber powder, acrylic fiber powder, glass balloon, shirasu balloon, coal powder,
Fillers such as acrylic resin powder, phenol resin powder, metal powder, ceramic powder, zeolite, slate powder, etc. (9)
Deodorants such as activated carbon, zeolite, silica sol, and silica gel (10) carbon black, titanium oxide, red iron oxide,
Pigments or dyes such as lead red, para red, navy blue, etc., (11) solvents such as ethyl acetate, toluene, alcohols, ethers, ketones, etc., (12) foaming agents, (13) defoamers, (14) dehydrating agents , (1
5) Antistatic agents, (16) antibacterial agents, (17) fungicides, (18) viscosity modifiers, (19) fragrances, (20) flame retardants and the like can be added. The compounding amount of these additives is 0 to 50% by weight based on the resin.

[0030]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Parts in Examples and Comparative Examples represent parts by mass. Also,
The test method of the evaluation items in the examples is as follows. [Tensile strength]: The composition shown in Table 1 was allowed to stand for 7 days in an atmosphere of 25 ° C and 65% RH and cured, and then the tensile strength at 25 ° C was measured according to JIS K7113. [Tensile Elongation]: The compositions shown in Table 1 were allowed to stand in an atmosphere of 25 ° C. and 65% RH for 7 days and cured, and then the tensile elongation at 25 ° C. was measured according to JIS K7113. [Adhesive strength]; The composition shown in Table 1 was coated on a surface of a 30 × 30 × 5 cm sidewalk PC board at 25 ° C. with a wool roller B-23 to a thickness of 1.5 mm at a temperature of 25 ° C. and 65% RH. After curing and curing in an atmosphere for 7 days, it was measured by the Kenken-type adhesive strength test method. (Unit: Kgf / cm ² ) [Cross-cut test];
μ, and apply under 25 ° C, 65% RH atmosphere.
After curing and curing for one day, a grid test was performed according to JISA5400.

Example 1 A cyclic dithiocarbonate compound 5-
(2-ethylhexyloxymethyl) -1,3-oxathiolan-2-thione (molecular weight 262, heterocyclic equivalent 2
62) (1 mol) was charged and stirred, and while keeping the inside of the reaction vessel at 30 ° C. or lower, Jeffamine D-
230 (manufactured by Sun Techno Chemical Co .; polyoxymethylenediamine, molecular weight 240, active hydrogen equivalent 60) is 240
After dropping g (1 mol), the mixture was aged at 40 ° C. for 2 hours. 200 mPa · s viscosity at 25 ° C, thiol equivalent 2
Thus, 50 pale yellow liquid hetero group-containing compounds (T-1) were obtained. Example 2 A cyclic trithiocarbonate compound 5-
828 g (6 mol) of methyl-1,3-oxathiolan-2-thione (molecular weight: 138, heterocyclic equivalent: 138)
And 1000 ml of tetrahydrofuran and stirred and dissolved therein, and while maintaining the inside of the reaction vessel at 40 ° C. or lower, Sannics SP-750 (manufactured by Sanyo Chemical Industries; sorbitol polyoxymethylene hexaol, molecular weight 750, OH-V).
125) was added dropwise at 750 g (1 mol),
For 2 hours. Viscosity at 25 ° C 12000mPa
A pale yellow liquid hetero group-containing compound (T-2) having a thiol equivalent of 263 was obtained.

Test Examples 1 to 3 and Comparative Test Example 1 Each component was mixed and stirred at the compounding amounts shown in Table 1, and the performance evaluation test as a resin modifier was performed by the above-mentioned test method. It is shown in FIG. The following epoxy resins were used. Epoxy resin; Epicoat 828 (manufactured by Yuka Shell Epoxy; bisphenol A diglycidyl ether, epoxy equivalent 190, viscosity 11 Pa · s) Epoxy resin curing agent: MXDA (manufactured by Mitsubishi Gas Chemical Company; meta-xylylenediamine active hydrogen equivalent 36, Viscosity 7mPa
・ S)

[0033]

[Table 1]

[0034]

The resin modifier of the present invention has the following effects. (1) Improve the flexibility and toughness of the resin to be modified. (2) Improve the adhesive strength of the resin to be modified.

Continued on the front page F-term (reference) 4J002 AA011 AA021 AA031 BB031 BB121 BC031 BD031 BD101 BD121 BE041 BF021 BG041 BG051 BG101 BL011 CB001 CC031 CC101 CC121 CC161 CC181 CD001 CF011 CF211 CG001 FD001 CH011 CH052010 FD090 FD130 FD200 FD320 4J005 AA04 AA08 BD05 BD06 4J030 BA20 BA42 BB02 BB06 BB09 BC02 BC08 BF10 BG13 CA01

Claims (4)

[Claims] 1. A resin modifier comprising a compound (A) represented by the following general formula (1). Embedded image [In the formula, X ¹ , X ² and X ³ are each independently an oxygen or sulfur atom; Y ¹ is —NR ³ — (R ³ is hydrogen or a group having 1 to 3 carbon atoms.
At least one divalent structure selected from the group consisting of an oxygen atom and a sulfur atom; Y ² and Y ³ are a direct bond or —NR ³ — (R ³ is hydrogen or alkyl having 1 to 3 carbon atoms) Group), an oxygen atom and a sulfur atom, at least one divalent structure; Z ¹ is hydrogen, —NHR ³ (R
³ is hydrogen or an alkyl group having 1 to 3 carbon atoms), at least one monovalent structure selected from the group consisting of a hydroxyl group and a mercapto group; R ¹ is a straight-chain structure which may contain an ether bond having 2 to 28 carbon atoms. A chain or branched hydrocarbon group; R ₂ is a direct bond or a monovalent to octavalent organic group having a molecular weight of 14 to 20,000;
AO is a group in which an alkylene (C2-4) oxide is opened; k and l are each independently 0 or an integer of 1 to 200;
m and n each represent a valence, m is an integer of 1 to 8, n is 0 or 1 to 7
And m + n represents an integer of 1 to 8] 2. In the general formula (1), X ³ is S, R ²
Is a direct bond or a divalent organic group having a number average molecular weight of 28 to 500. 3. In the general formula (1), X ² is O, Y ¹
Is -NH-. 4. In the general formula (1), R ² , Y ² , Y
^3. The resin modifier according to claim 1, wherein ³ is a direct bond, k and l are 1 ≦ k + 1 ≦ 200, and AO is a group in which ethylene oxide and / or propylene oxide is ring-opened.