JPH051123A - Unsaturated polyester resin composition, sheet-shaped molding material using the same, molding method and molded article - Google Patents

Abstract

(57) [Summary] [Structure] (A) Unsaturated polyester containing 1,4-butanediol and unsaturated dicarboxylic acid as main components, and (B)
Melt viscosity at 80 ℃ consisting of polymerizable unsaturated monomer is 1
An unsaturated polyester resin composition for a sheet-shaped molding material, a molding material using the same, and a molding method thereof, wherein the porosity is 00 poise or less. [Effect] The present invention provides flexibility at room temperature, compatibility with styrene monomer, film peeling property of the molding material and 40-
Since it has excellent fluidity at a medium temperature of 80 ° C., it is possible to provide a sheet-shaped molding material suitable for medium temperature molding by open molding. Furthermore, since it is possible to provide a new molding method capable of shaping into a mold at a medium temperature, a reduced pressure, and a contact pressure, it is possible to achieve industrial significance such as capital investment and energy saving. In addition, since it is possible to easily and cleanly cut off the volatile odor of the monomer and fix it to the mold, the work environment is excellent, the work environment problem can be solved, and the efficiency of the FRP molding cycle can be improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin composition, a sheet-shaped molding material using the same, a molding method and a molded article thereof, and more particularly, conventional high temperature high pressure molding using injection molding or pressing. , A crystalline unsaturated polyester resin excellent in flexibility at room temperature, compatibility with styrene, and physical properties after medium-temperature molding to enable a medium-temperature molding method of 40 to 80 ° C. The present invention relates to a composition, a fiber-reinforced sheet-shaped molding material using the composition, a molding method, and a molded product.

[0002]

2. Description of the Related Art The following are known as crystalline unsaturated polyester resins and molding materials used in conventional FRP molding methods such as injection molding and SMC press molding. For example, JP-A-48-26282. In the publication, the glycol component is composed of at least 70 mol% or more of ethylene glycol, and the acid component is 25 to 50 mol% of unsaturated dicarboxylic acid.
And a crystalline unsaturated polyester resin composition comprising an unsaturated polyester comprising 75 to 50 mol% of a saturated dicarboxylic acid and at least 80 mol% of a saturated dicarboxylic acid being terephthalic acid, and a polymerizable monomer is disclosed.

JP-A-55-92719 discloses that
4-Butanediol / other glycols = 7 / 3-10 / 0, terephthalic acid / fumaric acid = 5 / 5-1 / 9, and for injection molding materials consisting of styrene-based monomers and allyl-based monomers Resin compositions are disclosed.

Further, in JP-A-58-67709, a crystalline unsaturated polyester composed of 1,6-hexanediol / terephthalic acid / fumaric acid / polymerizable monomer is mixed with an amorphous unsaturated polyester. By doing
A molding compound that enables non-stickiness at room temperature without using a thickener such as O is disclosed.

Further, in JP-A-46-9945, at least 15 mol% of the glycol component is 1,3-.
Di (2-oxyalkoxy) benzene or 1,4-
A free-flowing crystalline unsaturated polyester resin composition which is solid at room temperature and is composed of di (2-oxyalkoxy) benzene, at least 25 mol% of which is an ethylenically unsaturated dicarboxylic acid, and a polymerizable monomer. The thing is disclosed.

Further, in a general fiber-reinforced sheet-shaped molding material, a mixture of a thermosetting resin, a glass fiber reinforcing material, and an inorganic filler is thickened with MgO or the like, or SMC or a fiber reinforcing material is impregnated with the thermosetting resin. There is a prepreg.

As a method for obtaining an FRP molded product, SMC, BMC
In addition to the high temperature compression molding method that requires a press like
There are a hand lay-up method and a spray-up method of molding with a liquid resin using an open mold.

[0008]

The crystalline unsaturated polyester resin used in the conventional SMC or injection molding material is used as the fiber-reinforced sheet-shaped molding material of the present invention in the open-mold pressure-reducing molding as follows. There's a problem. For example, the resin composition described in JP-A-48-26282 is a very brittle and hard solid even though it contains a styrene monomer, and has a flexible crystalline property such as that of the present invention. It cannot be a saturated polyester composition or a flexible sheet-shaped molding material, and this crystalline unsaturated polyester has poor compatibility with styrene-based monomers and allyl-based monomers when melted at high temperatures, resulting in uniform molding. It is very difficult to get the material. In addition, JP-A-55
The resin composition described in Japanese Patent Publication No. -92719 has good compatibility with styrene-based monomers and allyl-based monomers when heated and melted, but at room temperature as targeted by the present invention. A flexible crystalline unsaturated polyester resin cannot be obtained.

Further, the resin composition described in JP-A-58-67709 is obtained by mixing the crystalline unsaturated polyester with the amorphous unsaturated polyester, and thus at room temperature without using a thickener such as MgO. Although it discloses a molding compound that enables non-adhesiveness, it has a different structure, and since the obtained sheet-shaped molding material is used as a press molding material by SMC, it is a flexible sheet-shaped molding material at room temperature. Is not possible. Furthermore, JP-A-46-9945
The crystalline unsaturated polyester resin composition described in the publication cannot be used as a sheet-shaped molding material because it is used in a powder state even though it contains a polymerizable monomer, and is expensive as a raw material. Since glycol has to be used, it is disadvantageous in terms of economical efficiency in the case of mass production.

Conventional sheet-like molding materials such as SMC, which are conventionally known, are molded under a molding temperature of 100 to 160 ° C. and a molding pressure of 30 to 60 kg / cm ² , so that a male mold or a female mold is formed. Therefore, a pair of mold and an expensive press for supplying high pressure are required. For this reason, there have been drawbacks that a large initial cost is required and the shape of the molded product cannot be easily changed.

[0011]

Therefore, the present inventors have solved the above-mentioned various problems and can be used for a medium-temperature molding method replacing conventional high-temperature and high-pressure molding such as press molding by SMC and injection molding. As a result of continuing intensive research to develop a fiber-reinforced sheet-shaped molding material using crystalline unsaturated polyester as a raw material, 1,4-butanediol / fumaric acid system and 1,4-butanediol / terephthalic acid / fumaric acid system Add 1, 4 glycol components such as acid unsaturated polyester
-A crystalline unsaturated polyester resin composition having a specific melt viscosity obtained by replacing butanediol as a main component with an acid component by a symmetric saturated dicarboxylic acid or by substituting a glycol component with another symmetric glycol. To find a resin composition for a sheet-shaped molding material suitable for a vacuum molding method by an open mold, which has two contradictory properties of being flexible at room temperature, excellent in compatibility with a styrene monomer, and capable of peeling a film, and to complete the present invention. Arrived

That is, the present invention provides an unsaturated polyester resin composition comprising 1,4-butanediol as a glycol component, an unsaturated dicarboxylic acid as a main component as an acid component, and a saturated dicarboxylic acid if necessary in combination.
(B) When the saturated dicarboxylic acid is not used in combination with the acid component, 50 to 1 of 1,4-butanediol is contained in all glycol components.
When the saturated dicarboxylic acid is used in combination with the (b) acid component, (Rho 1) is a linear aliphatic symmetric saturated dicarboxylic acid, the total amount of 1,4
-Butanediol is 50 to 100 mol% and unsaturated dicarboxylic acid is 70 mol% or more in all acid components,
(Raw 2) When the aromatic symmetric saturated dicarboxylic acid is used in combination, 1,4-butanediol is 5 in all glycol components.
0 to 100 mol% (rho 3), when the combined use is a linear aliphatic symmetric saturated dicarboxylic acid and an aromatic symmetric saturated dicarboxylic acid, 1,4-butanediol is 60 in the total glycol component. 80 ° C composed of unsaturated polyester (A) consisting of ~ 100 mol% and polymerizable monomer (B)
A crystalline unsaturated polyester resin composition having a melt viscosity of 100 poise or less, and a sheet-like molding material comprising the same and a fiber reinforcement,
The present invention provides a molding method characterized by using it in an open mold, and a molded article characterized by using the molding material.

(Structure) The composition of the present invention has a viscosity of a solution of a styrene monomer containing 66% by weight of a crystalline unsaturated polyester of 100 poise or less at 80 ° C., preferably 10 poise or less, and a melt viscosity at 50 ° C. Preferably 50
It is a resin composition for a sheet-shaped molding material of a medium temperature molding method of poise or less.

In the unsaturated polyester of the present invention, 1,4-butanediol (abbreviated as 1,4-BG) is preferably used as a glycol component in an amount of 50 mol% or more, and an unsaturated dicarboxylic acid is used as an acid component. Is used as a main component in an amount of 50 mol% or more, and if necessary, a saturated dicarboxylic acid is used in combination.

When a saturated dicarboxylic acid is not used in combination with the acid component (a), 1,4-BG accounts for 50 to 50% of all glycol components.
It is 100 mol%, preferably 60 to 90 mol%. When using a saturated dicarboxylic acid together with the acid component (b), (rho 1)
When the combined use is a linear aliphatic symmetric saturated dicarboxylic acid, 1,4-BG in the total glycol component is 50 to 100 mol%, preferably 60 to 100 mol%, and the unsaturated dicarboxylic acid in the total acid component is Is 70 mol% or more. (Rho 2) When the aromatic symmetric saturated dicarboxylic acid is used in combination, 1,4-BG is 50 to 100 mol% in all glycol components. (Raw 3) When the linear aliphatic symmetric saturated dicarboxylic acid and the aromatic symmetric saturated dicarboxylic acid are used in combination, the amount of the linear aliphatic symmetric saturated dicarboxylic acid is preferably 30 mol% or less. , 1,4-BG is 6 in all glycol components
It is 0 to 100 mol%.

If the amount of other glycols is out of this range and the amount of other glycols is large, the unsaturated polyester becomes too hard at room temperature or too soft and does not become a sheet-like molding material with a bad tack, and the phase with the styrene as a polymerizable monomer does not occur. Solubility becomes poor. Further, if it is soft, it becomes considerably sticky at room temperature, and the resin may flow out from the cut portion during molding or the film may not be peeled off. If the melt viscosity at 80 ° C. is higher than 100 poise, the fiber-reinforced sheet-shaped molding material will be solidified during production, impregnation into the fiber-reinforced material or defoaming will be poor, and the yield rate of the molding material will be poor. Markedly reduced. Further, a high temperature is required at the time of molding, an energy cost and a risk are increased, and a mold capable of withstanding the high temperature is required.

The glycol component of the crystalline unsaturated polyester of the present invention contains 1,4-BG as an essential component and, if necessary, other symmetric glycol together. When ethylene glycol is mainly used without using 1,4-BG as a main component, the compatibility with styrene becomes poor.

Other symmetrical glycol components used in combination with 1,4-BG include, for example, ethylene glycol, neopentyl glycol, diethylene glycol and 1,5-
Pentanediol, 1,6-hexanediol, 2,2
Examples thereof include dimethyl-3-hydroxypropyl, 2,2-dimethyl-3-hydroxypropionate, hydrogenated bisphenol A, ethylene oxide or propion oxide adduct of bisphenol A, and the like.

Examples of the unsaturated dicarboxylic acid of the present invention include fumaric acid, maleic acid and maleic anhydride. Examples of the linear aliphatic symmetric saturated dicarboxylic acid of the present invention include oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid and the like.

Examples of the polymerizable monomer (B) used in the present invention include styrene, vinyltoluene, chlorostyrene, bromostyrene, t-butylstyrene, α-methylstyrene, divinylbenzene, acrylonitrile, methacrylonitrile, Examples thereof include esters of acrylic acid and methacrylic acid having 1 to 18 carbon atoms in the alcohol chain. Preferred is styrene.

The mixing ratio of the unsaturated polyester (A) of the present invention and the polymerizable monomer (B) is preferably (A) :( B) = 50.
70% by weight: 30 to 50% by weight.

The curing catalyst of the present invention is not particularly limited, and a generally known one can be used,
For example, methyl ethyl ketone peroxide, cyclohexane peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropyl peroxide, benzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, diethyl butyl peroxide. oxide,
Tert-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (benzoyl peroxide) hexane, lauroyl peroxide, stearoyl peroxide, benzoyl peroxide, tertiary butyl peroxide-2- Examples thereof include peroxide catalysts such as ethyl hexanoate and tertiary butyl peroxylaurate, and two or more kinds of these may be used in combination.

In addition to the peroxide catalyst, a photopolymerization initiator can be used, and the photopolymerization initiator is not particularly limited, and a generally known one can be used.
1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4- (methylthio) phenyl]
-2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4
Examples include -isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and acylphosphine oxide-based compounds. Of course, a peroxide catalyst and a photopolymerization initiator may be used in combination. The unsaturated polyester resin can be used generally in the range of 0.3 to 3 parts by weight based on 100 parts by weight.

As the curing accelerator, metal salts of organic acids, particularly cobalt salts such as cobalt naphthenate, cobalt octylate, and acetylacetone cobalt are used.
The sheet-shaped molding material of the present invention includes a fiber reinforcing material, a curing catalyst,
A film, if necessary, an inorganic filler, a pigment, an internal release agent, and a low-shrinking agent, and preferably has an ASKER (C-TYPE) hardness of 60 or less at 50 ° C.

The fiber reinforcing material used in the present invention is, for example, glass fiber, organic fiber such as amide, aramid, vinylon, polyester and phenol, carbon fiber, metal fiber, ceramic fiber or a combination thereof.
Glass fiber and organic fiber are preferable. The form of the fiber may be plain weave, satin weave, matte or the like, but matte is preferred from the viewpoint of construction method, thickness keeping and the like. It is also possible to cut glass roving into a length of 20 to 100 mm and use it as chopped strands.

The addition amount is preferably 20 in the molding material.
-40% by weight.

Examples of the internal mold release agent include higher fatty acids such as stearic acid and zinc stearate, and conventionally known ones such as higher fatty acid esters and alkyl phosphates. 100 parts by weight of unsaturated polyester resin can be used. On the other hand, it can usually be used in a proportion of 0.5 to 5 parts by weight.

The shrinkage reducing agent is a thermoplastic resin, and specific examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate,
Lower alkyl esters of acrylic acid or methacrylic acid such as ethyl acrylate, homopolymers or copolymers of monomers such as styrene, vinyl chloride, vinyl acetate, at least one of the vinyl monomers, and lauryl methacrylate , Isovinyl methacrylate, acrylamide,
In addition to copolymers of at least one monomer consisting of methacrylamide, hydroxylalkyl acrylate or methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, cetylstearyl methacrylate, cellulose acetate butyrate and cellulose acetate propio Nate, polyethylene, polypropylene, etc.

Examples of the inorganic filler used in the sheet-shaped molding material of the present invention include calcium carbonate, silica, china clay, dolomite, talc, barite, aluminum hydroxide and the like, and two or more kinds may be used in combination. .

In the sheet-shaped molding material of the present invention, the resin composition is applied to a film (polyvinyl alcohol or the like), glass chopped strands are cut to an arbitrary length and scattered, and the resin is applied separately thereon. It is manufactured by covering the film with the film and impregnating it with a roller or the like to defoam it.

The open mold molding method of the sheet-shaped molding material of the present invention is to seal and fix the periphery of the fiber reinforced sheet-shaped molding material around the molding die, and depressurize the material and the cavity closed by the molding die. , After bringing the molding material into close contact with the mold,
It is a vacuum molding method of shaping and curing.

More specifically, in the vacuum molding method by the open mold used in the present invention, the film reinforced sheet-like molding material of the present invention capable of peeling a film at room temperature and having a certain degree of flexibility is used to prepare the following (1), It is done by the method of (2).

(1) After directly fixing the periphery of the fiber-reinforced sheet-shaped molding material to the periphery of the molding die, or sealing and fixing the fiber-reinforced sheet-shaped molding material fixed by a frame while heating to the periphery of the molding die. After that, it is preferably heated at 40 to 80 ° C., and the molding material and the cavity closed by the molding die are decompressed to bring the molding material into close contact with the mold to cure the molding method.

(2) The molding method according to (1), characterized in that only the plastic film on the molding die side of the fiber-reinforced sheet-shaped molding material is peeled off and then molded. The sheet-shaped molding material according to the present invention can be subjected to medium temperature molding even in the conventional press molding.

[0035]

EXAMPLES The present invention will be described in detail below with reference to synthesis examples, examples and comparative examples, but "parts" and "%" are based on weight.

Example 1 (Synthesis of Unsaturated Polyester UP-1) A reaction vessel equipped with a stirrer, a reflux cooling tower, a nitrogen gas inlet tube, and a thermometer is shown in Table-1.
Charge the molar ratio of UP-1 shown in the figure to 20 ° C and raise to 20 ° C.
The reaction proceeds at 5 ° C., the temperature in the reaction vessel is lowered with an acid value of 20, and 0.01 part of hydroquinone and 0.01 part of tert-butylcatechol are added with respect to the total amount charged.
05 parts were charged to obtain unsaturated polyester UP-1.

The crystalline unsaturated polyester resin obtained by adding 34% of a styrene monomer to the UP-1 had a melt viscosity at 80 ° C. of 1.30 poise by a BM type viscometer. (Preparation of sheet-like molding material) A crystalline unsaturated polyester resin composition obtained by adding 34% of styrene monomer to UP-1 was used as a photopolymerization initiator under heating at 50 ° C (Ciba Geigy product, Irga Cure 651) 1% blended, 30
After coating on a polyvinyl alcohol film having a thickness of micron and spraying 2 inches of glass chopped strands, the composition is further coated with a polyvinyl alcohol film having a thickness of 30 microns, which is a glass chopped strand side. After being impregnated with a cover roller and the like to remove the bubbles, the mixture was cooled to room temperature to obtain a fiber-reinforced sheet-shaped molding material A-1.

The molding material A-1 had a thickness of 3.0 mm, a glass chopped strand content of about 30% and an ASKER (TYPE-C) hardness of 58 at 50 ° C. (Molding) The obtained sheet-shaped molding material A-1 was clamped and fixed to the FRP mold shown in Fig. 1 with a clamp, and the void between the mold and the sheet-shaped molding material was shaped at 50 ° C under a reduced pressure of 400 mmHg. Let
After irradiation with an ultraviolet lamp for 5 minutes, a molded product B-1 was obtained.

Example 2 (Synthesis of unsaturated polyester UP-2) UP-2 was obtained in the same manner as in Example 1 except that the molar ratio of UP-2 shown in Table-1 was used.

The melt viscosity at 80 ° C. of the crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-2 was 1.08 poise with a BM type viscometer. (Preparation of sheet-shaped molding material) A fiber-reinforced sheet-shaped molding material A-2 was obtained in the same manner as in Example 1 except that UP-2 was mixed with 2% of benzoyl peroxide paste (50% dibutyl phthalate) at room temperature. It was A-2 has a thickness of 3.0 mm and contains about 30% glass chopped strands.
At 50 ° C, the ASKER (TYPE-C) hardness was 43.

(Molding) The obtained sheet-shaped molding material A-2 was clamped around the periphery of the FRP mold shown in FIG. 1 at 40 ° C., and a space between the sheet-shaped molding material and the mold was provided under a reduced pressure of 400 mmHg. It was shaped, heated to 80 ° C., held for 10 minutes and cured to obtain a molded product B-2.

Example 3 (Synthesis of unsaturated polyester UP-3) UP-3 was obtained in the same manner as in Example 1 except that the molar ratio of UP-3 shown in Table 1 was used. UP
The melt viscosity at 80 ° C. of the crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to -3 is
It was 0.74 poise with a BM type viscometer.

(Preparation of sheet-shaped molding material) Using a crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-3, a fiber-reinforced sheet-shaped molding material was prepared in the same manner as in Example 1. Got A-3. A-3 has a thickness of 3.0 m
m, and the content of glass chopped strands is about 3
The ASKER (TYPE-C) hardness at 50% at 0% was 36.

(Molding) A molded product B-3 was obtained in the same manner as in Example 1 using the obtained sheet-shaped molding material A-3.

Example 4 (Synthesis of Unsaturated Polyester UP-4) In a reaction vessel equipped with a stirrer, a reflux cooling tower, a nitrogen gas introducing tube, and a thermometer, the molar ratio of UP-4 shown in Table 1 and , An esterification catalyst (1000 ppm relative to the charged amount) was charged, the reaction proceeded at 205 ° C and the acid value was
The temperature was lowered at 1 to obtain 0.01 parts by weight of hydroquinone and 0.005 parts by weight of tert-butyl catechol in the total amount of UP-4.

The melt viscosity at 80 ° C. of the crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-4 was 0.60 poise with a BM type viscometer. (Preparation of sheet-shaped molding material) A crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-4 was heated at 50 ° C. under a photopolymerization initiator (Irgacure 65
1) 1% was blended and applied on a polyvinyl alcohol film having a thickness of 30 microns, sprayed with 2 inches of glass chopped strands, and then a polyvinyl alcohol film having a thickness of 30 microns coated with this formulation. This composition was covered with a roller such as a cover so that it came to the glass chopped strand side, defoamed, and then cooled to room temperature to obtain a fiber-reinforced sheet-shaped molding material A-1. A-4
Has a thickness of 3.0 mm, the content of glass chopped strands is about 30%, and ASKER (TYPE-
C) The hardness was 46. (Molding) The obtained sheet-shaped molding material A-4 was clamped around the periphery of the FRP mold shown in FIG. 1, and the space between the mold and the sheet-shaped molding material was shaped at a reduced pressure of 400 mmHg at 50 ° C. After irradiation with a lamp for 5 minutes, a molded product B-4 was obtained.

Example 5 (Synthesis of Unsaturated Polyester UP-5) UP-5 was obtained in the same manner as in Example 4 except that the molar ratio of UP-5 shown in Table 1 was used.

The melt viscosity at 80 ° C. of the crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-5 was 0.75 poise with a BM type viscometer. (Preparation of sheet-shaped molding material) Using a crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-5, a fiber-reinforced sheet-shaped molding material A-5 was prepared in the same manner as in Example 4. Got A-5 has a thickness of 3.0 mm, and the glass chopped strand content is about 30% at 50 ° C.
The ASKER (TYPE-C) hardness was 44.

(Molding) Same as Example 4 except that the obtained fiber reinforced sheet-shaped molding material A-5 was applied with a gel coat in advance and cured to remove the film on the mold side surface of the molding material A-5. Molded and cured by the method of 1 to obtain a gel-coated molded product B-5.

Example 6 (Synthesis of unsaturated polyester UP-6) UP-6 was obtained in the same manner as in Example 4, except that the molar ratio of UP-6 shown in Table 1 was used. UP
The melt viscosity at 80 ° C. of the crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to -6 is
It was 1.80 poise with a BM type viscometer.

(Preparation of sheet-shaped molding material) Using a crystalline unsaturated polyester resin composition obtained by adding 34% of styrene monomer to UP-6, a fiber-reinforced sheet was prepared in the same manner as in Example 4. A molding material A-6 was obtained. A-6 has a thickness of 3.0 mm, a glass chopped strand content of about 30%, and an ASKER (TYPE-C) hardness of 3 at 50 ° C.
It was 2.

(Molding) Using the obtained sheet-shaped molding material A-6, a molded product B-6 was obtained in the same manner as in Example 4.

Comparative Example 1 (Synthesis of Unsaturated Polyester UP-7) UP-7 was obtained in the same manner as in Example 1 except that the molar ratio of UP-7 shown in Table 1 was used.
The melt viscosity at 80 ° C. of the crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-7 was 420 poise with a BM type viscometer.

(Preparation of Sheet-Shaped Molding Material) A crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-7 was mixed with 1% of a photopolymerization initiator under heating at 50 ° C., After application on a 30 micron thick polyvinyl alcohol film and sprinkling with 2 inches of glass chopped strands, the formulation was further applied 30
The composition was covered with a micron-thick polyvinyl alcohol film so that it came to the glass chopped strand side, impregnated with a roller, etc. and defoamed, but solidification occurred during this work and a uniform sheet-like molding material was obtained. I couldn't do it.

Comparative Example 2 (Synthesis of Unsaturated Polyester UP-8) UP-8 was obtained in the same manner as in Example 4 except that the molar ratios shown in Table-1 were used. The melt viscosity at 80 ° C. of the crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-8 was 125 poise by a BM type viscometer.

(Preparation of sheet-like molding material) Using a crystalline unsaturated polyester resin obtained by adding 34% of styrene monomer to UP-8, a fiber-reinforced sheet-like molding material was prepared in the same manner as in Example 4. Got A-8. A-8 has a thickness of 3.0m
m, and the content of glass chopped strands is about 3
The ASKER (TYPE-C) hardness at 0 ° C and 50 ° C was 84.

(Molding) The obtained sheet-shaped molding material A-8 was clamped around the periphery of the FRP mold shown in Fig. 1 and the gap between the mold and the sheet-shaped molding material was reduced to 400 mmHg at 50 ° C. Attempts were made to shape it, but it began to solidify during shaping and a uniform molded product could not be obtained.

Comparative Example 3 (Synthesis of Unsaturated Polyester UP-9) UP-9 was obtained in the same manner as in Example 4 except that the molar ratios shown in Table-1 were used. As in Comparative Example 1, the melt viscosity at 80 ° C. was 0.30 poise by a BM type viscometer.

(Preparation of sheet-shaped molding material) A fiber-reinforced sheet-shaped molding material was prepared in the same manner as in Example 4. However, the unsaturated polyester resin composition did not show crystallinity even after a long time, and it was not possible to obtain a sheet strip molding material capable of peeling a film.

Comparative Example 4 (Synthesis of Unsaturated Polyester UP-10) UP-10 was obtained in the same manner as in Example 4 except that the molar ratio shown in Table 1 was used. Comparative Example 1
Similarly, the melt viscosity at 80 ° C. was 0.70 poise with a BM type viscometer.

(Preparation of sheet-shaped molding material) A fiber-reinforced sheet-shaped molding material was prepared in the same manner as in Example 4. However, the unsaturated polyester resin composition did not show crystallinity even after a long time, and it was not possible to obtain a sheet-like molding material capable of peeling a film.

Comparative Example 5 (Synthesis of Unsaturated Polyester UP-11) UP-11 was obtained in the same manner as in Example 4 except that the molar ratios shown in Table-1 were used. As in Comparative Example 1, the melt viscosity could not be measured because it did not dissolve uniformly in the styrene monomer.

(Preparation of sheet-shaped molding material) A fiber-reinforced sheet-shaped molding material was prepared by the same method as in Example 4, but the unsaturated polyester resin composition was not mixed, so that a sheet-shaped molding material was obtained. I couldn't.

The above resin raw material ratios are shown in Table 1, the evaluation of the resin composition is shown in Table 2, and the evaluation of the sheet-like molding material is shown in Table 3.

[0065]

[Table 1]

EG: ethylene glycol BG: 1,4-butanediol HG: 1,6-hexanediol AA: adipic acid TPA: terephthalic acid FA: Fumaric acid

[0067]

[Table 2] Softening temperature (° C.): Solid softening temperature of unsaturated polyester (UP) Compatibility: A mixed state of styrene monomer and unsaturated polyester was observed. ◯: Uniformly dispersed and good compatibility, Δ: Uniformly dispersed and slightly poor compatibility, Poor compatibility: Poor incompatibility without uniform dissolution Flexibility: Softness at room temperature was indicated by the feel of a finger. ◎: Flexible and no tack, ○: Flexible and slightly tacky, ×: Too hard, or tacky and too soft

[0068]

[0069]

[Table 4]

Example 7 (Fabrication of Flat Plate and Strength Test) The periphery of the sheet-shaped molding material of A-1 and A-4 was closely adhered and fixed to the flat plate, and the void portion between the sheet-shaped molding material and the flat plate was decompressed. Shaped and cured, glass content approx.
FRP flat plates C-1 and C-2 having a thickness of 30% and a thickness of about 3 mm were obtained.

The strength test is performed according to JIS-K-6911 and the results are shown.
-5.

Comparative Example 6 (Preparation of flat plate and strength test) Unsaturated polyester resin 80
10 (Dainippon Ink and Chemicals Co., Ltd. product) and 6% cobalt naphthenate 4 parts by weight, 55% MEKPO 1 part by weight, glass content about 30% by hand lay-up using 2 inch glass chopped strands, An FRP flat plate C-3 having a thickness of about 3 mm was obtained.

The strength test is performed according to JIS-K-6911 and the result is shown.
-5.

Comparative Example 7 (Preparation of flat plate and strength test) Molding temperature using Dickmat-2550 (SMC manufactured by Dainippon Ink and Chemicals, Inc.)
An FRP plate having a glass content of about 30% and a thickness of about 3 mm was obtained at 140 ° C., a charging area of 70%, a molding pressure of 100 kg / cm ² , and a pressing time of 5 minutes.

The strength test was performed according to JIS-K-6911 and the results are shown in Table-5.

[0076]

[Table 5]

[0077]

The unsaturated polyester resin composition of the present invention has excellent compatibility with styrene monomers, flexibility at room temperature and excellent non-adhesiveness.

Further, according to the present invention, by using this crystalline unsaturated polyester resin composition, it is excellent in flexibility at room temperature, solidity, film peeling property and fluidity at a medium temperature of 40 to 80 ° C. It provides a new fiber-reinforced sheet-shaped molding material, and because it is a flexible sheet-shaped molding material, it can be used for vacuum molding by the open-mold molding method that does not require a heavy mold that can withstand high temperatures and high pressures. Since it is possible to provide a new molding method that can be molded into a mold with reduced pressure and contact pressure, it is possible to achieve industrial significance such as capital investment and energy saving.

Further, since the conventional FRP molding method such as hand lay-up and spray-up has a problem of monomer volatilization odor, etc., cutting and fixing to a mold can be performed easily and cleanly, which is excellent in working environment. Solving work environment problems and FRP
The efficiency of the molding cycle can be improved.

[Brief description of drawings]

FIG. 1 is a cross-sectional view in which a sheet-shaped molding material is attached to an open mold forming die used in an example of the present invention, and a top view of the forming die.

[Explanation of symbols]

1 Sheet-shaped molding material 2 FRP open mold forming die 3 fixed frame 4 clamps 5 space parts 6 decompression port

Claims (4)

[Claims] 1. An unsaturated polyester resin composition comprising 1,4-butanediol as a glycol component, an unsaturated dicarboxylic acid as a main component as an acid component, and a saturated dicarboxylic acid in combination, if necessary. When the saturated dicarboxylic acid is not used together, 50 to 1 of 1,4-butanediol is contained in all glycol components.
When the saturated dicarboxylic acid is used together with the (b) acid component, (Rho 1) when the combined use is a linear aliphatic symmetric saturated dicarboxylic acid, 1,4- 50 to 100 mol% of butanediol and 70 mol% or more of unsaturated dicarboxylic acid in all acid components, (Raw 2) when used in combination with aromatic symmetric saturated dicarboxylic acid, in all glycol components , 1,4-butanediol is 5
0 to 100 mol%, and when (Rho 3) is used in combination with a linear aliphatic symmetric saturated dicarboxylic acid and an aromatic symmetric saturated dicarboxylic acid, 60 parts of 1,4-butanediol are contained in all glycol components. An unsaturated polyester (A) consisting of ~ 100 mol%,
The melt viscosity of the polymerizable monomer (B) at 80 ° C is 1
A crystalline unsaturated polyester resin composition characterized by having a poise of not more than 00 poise. 2. A sheet-shaped molding material comprising the crystalline unsaturated polyester resin composition according to claim 1 and a fiber reinforced material. 3. A molding method, wherein the molding material according to claim 2 is used in open molding. 4. A molded article comprising the molding material according to claim 2.