JP5296298B2 - Crystalline resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that is low viscous in a heat-melted state and crystallizes in a short time when cooled from the heat-melted state, and its manufacturing method. <P>SOLUTION: Allyl alcohol of 116 g and di-n-butyltin dilaurate of 0.06 g as a urethanization catalyst were added into a container and agitated, and the temperature was raised to 70&deg;C. Then, 168 g of hexamethylene diisocyanate was added dropwise. The liquid reaction mixture was solidified and crystallized to give a crystalline monomer/oligomer. This compound of 40 pts.wt. and a crystalline unsaturated polyester of 60 pts.wt. were heat-melted and mixed. The resultant mixture was low viscous. The mixture was cooled to an ordinary temperature and was instantaneously solidified and crystallized, to give the resin composition. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a resin composition used as a molding material or the like in the fields of, for example, electricity, electronics, automobile parts, and building materials, and a method for producing the same.

Conventionally, attempts have been made to use crystalline unsaturated polyester resins as molding materials such as injection molding, press molding by BMC, SMC, and open molding (see Patent Document 1). The crystalline unsaturated polyester resin is solid at room temperature, but in the various molding steps described above, the crystalline unsaturated polyester resin once becomes liquid by heating and melting, and then solidifies again when cooled to room temperature.
JP-A-48-26282

  However, the conventional crystalline unsaturated polyester resin has a problem that it is difficult to handle because it has a high viscosity when heated and melted. Further, the conventional crystalline unsaturated polyester resin has a high melting point, and even if it is once melted by heating and then cooled to room temperature, it may take 2-3 days to crystallize. For this reason, there has been a problem that after molding, a process such as waiting for the crystalline unsaturated polyester resin to solidify or aging is required. In addition, because of its high viscosity, it may be diluted with liquid styrene monomer, etc. In that case, liquid styrene monomer is present in the solidified product even after solidification. Had a negative effect.

  The present invention has been made in view of the above points, and has a low viscosity when heated and melted, extremely low volatility, and a resin composition that solidifies in a short time when cooled from a heated and melted state, and a method for producing the same The purpose is to provide.

(1) The invention of claim 1
And it represented Ru crystalline monomer oligomer (A) in formula (1), seen containing an unsaturated polyester (B), the crystalline resin composition crystal solidified at room temperature.
However, R < ₁ > is group represented by Formula (2) or Formula (3), and R < ₂ >, R < ₃ > is group represented by Formula (4) or Formula (5) .

By including the component (A), the crystalline resin composition of the present invention has a low viscosity when heated and melted, and is easy to handle. Therefore, the viscosity can be reduced without using a styrene monomer or the like.

  The crystalline resin composition of the present invention is solid at ordinary temperature (room temperature, 20 ° C.), but melts when heated. Then, when it cools (for example, it cools to normal temperature), it crystallizes in a short time by including the said (A) component. Therefore, if the crystalline resin composition of the present invention is used as a molding material, a process of waiting for a long time until recrystallization after molding, as in the case of a conventional crystalline polyester resin, becomes unnecessary. In addition, the component (A) is solid at room temperature and is not liquid at room temperature like styrene monomer, so there is no odor or emission, and it is not harmful to human body or environment.

The component (A) is a solid crystal at normal temperature. In the above formula (1) representing the component (A), it is preferable that (R ₂ —O—) and (R ₃ —O—) are located on the opposite side when viewed from R ₁ . With such a positional relationship, the crystalline resin composition is more easily solidified at room temperature. The molecular weight of the component (A) is preferably in the range of 142 to 4000. The melting point of the component (A) is preferably in the range of 25 to 140 ° C, particularly preferably in the range of 30 to 110 ° C.

In the above formula (1) representing the component (A), R ₁ preferably has a structure in which the molecule is linear and has no branching. Further, as R ₁ , for example, a divalent linear hydrocarbon such as a group represented by the formula (2), which is bonded to a urethane group on both sides thereof is preferable. R ₁ is preferably a divalent and bilaterally symmetric group such as the group shown in Formula (2) or Formula (3) .

R ₂ and R ₃ preferably have a structure in which the molecule is not branched on a straight line. R ₂ and R ₃ may be the same group or different groups. One or both of R ₂ and R ₃ have an unsaturated bond . R _2, R ₃ are as group bonding to oxygen radicals, for example, can have a CH _2.

The component (B) (unsaturated polyester) contained in the crystalline resin composition of the present invention is preferably a crystalline solid at room temperature (20 ° C.), but it may be liquid or glass solid at room temperature. Good. As a crystalline solid at normal temperature, for example, any one or more of the following group of unsaturated dibasic acids is used as the acid component, and any one or more of the following group of raw material glycols as the glycol The thing using is mentioned. Furthermore, any one or more of the saturated dibasic acid group may be used depending on the intended use.
(Group of unsaturated dibasic acids)
Fumaric acid, maleic anhydride, itaconic acid (group of saturated dibasic acids)
Adipic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, het acid (chlorendic acid), tetrabromophthalic anhydride (group of glycols of raw material) )
Ethylene glycol, 1,4 butanediol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol, bishydroxyethyl terephthalate, 2,2-bis (4-polyoxyethylene-oxyphenyl) propane, propylene glycol, diethylene glycol, di Propylene glycol, neopentyl glycol, 1,3 butanediol, 1,6 hexanediol, bisphenol A propylene oxide adduct, dibromoneopentyl glycol, pentaerythritol diallyl ether, allyl glycidyl ether As saturated polyester, what is described in Unexamined-Japanese-Patent No. 2003-183368 is mentioned, for example. That is, 25 to 45 mol% (preferably 30 to 40 mol%) of terephthalic acid and 55 to 75 mol% (preferably 60 to 70 mol%) of fumaric acid are used as the main components as the acid component, and other components are necessary. In addition, 0 to 8 mol% (preferably 0 to 6 mol%) of the dicarboxylic acid is used in combination, and 92 to 100 mol% (preferably 94 to 100 mol%) of 1,4-butanediol is the main component as the glycol component. And, if necessary, another glycol is used in combination with 0 to 8 mol% (preferably 0 to mol%).

The unsaturated polyester can be produced by a conventional method. In addition, the production of the crystalline solid unsaturated polyester at room temperature includes, for example, JP-A No. 2003-183368, JP-A No. 49-131289, JP-A No. 50-102688, JP-A No. 60-49221. It can be performed by the method described in the publication. That is, after adding a catalyst to terephthalic acid and other dicarboxylic acids and 1,4-butanediol and other glycols, esterification is performed by heating according to a conventional method, or after transesterification using dimethyl esters, Fumaric acid and other dicarboxylic acids are added and dehydration condensation polymerization is performed under a nitrogen stream. In the latter stage of the condensation polymerization step, the reduction compression polymerization may be performed using a vacuum pump.
(B) As for the molecular weight of a component (unsaturated polyester), the range of 1000-30000 is suitable.

  In the present invention, the blending ratio (weight ratio) between the component (A) and the component (B) is preferably in the range of (A) / (B) = 95/5 to 5/95, and 90/10 to 10 / A range of 90 is more preferred. In particular, in the case of an unsaturated polyester in which the component (B) is a crystalline solid at room temperature, a range of 5/95 to 80/20 is preferable. By increasing the proportion of the component (A), the viscosity becomes lower at the time of melting, and it becomes easier to form a solid crystal at room temperature. In particular, when the unsaturated polyester is liquid at room temperature, the composition can be made harder at room temperature by increasing the proportion of component (A).

  As a method for producing the crystalline resin composition of the present invention, for example, the crystalline solid (A) component and the (B) component (crystalline solid or liquid, glassy) are mixed, heated and melted. There is a method of mixing uniformly and then cooling to room temperature to solidify the crystal. Alternatively, the components (A) and (B) may be heated and melted, mixed, and then cooled to room temperature for solidification.

  The crystalline resin composition of the present invention may contain, for example, a polymerization initiator in addition to the components (A) and (B). The polymerization initiator is used to start polymerization of a site (for example, ethylenically unsaturated bond portion) that causes a polymerization reaction among the components (A) and (B), and is selected according to the curing mode to be employed. be able to.

  For example, in the case of medium temperature curing, diisopropyl peroxydicarbonate, benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxyneodikenate, azobisisobutyronitrile, azobisdiethylvaleronitrile In the case of high-temperature curing, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl perbenzoate, dicumyl peroxide, etc. are used. In the case of UV curing, benzophenone-based, benzoin ether-based Anthraquinone compounds and the like are used.

  In addition, the crystalline resin composition of the present invention can contain any component that meets the required performance. Specific examples of such components include, for example, fillers (calcium carbonate, aluminum hydroxide, resin powder, pulp, etc.), reinforcing agents (glass fibers, carbon fibers, metal fibers, whiskers, etc.), ultraviolet absorbers (benzophenone). System, salicylate system, benzotriazole system, acrylonitrile system, metal rust salt system, hindered amine system, etc.), foaming agent (inorganic system, organic system), flame retardant, antistatic agent, lubricant, colorant, solvent, antioxidant Agents, plasticizers (DOP, DBP, etc.), other thermoplastic resins, other thermosetting resins, and the like.

  The crystalline resin composition of the present invention can be used for various applications as shown below. In order to prepare normal SMC and BMC prepregs, an unsaturated polyester is diluted with a styrene monomer, and various additives, fillers, reinforcing agents, curing agents, and metal bond crosslinking agents such as active magnesia are added. By aging for a long time, gelling, thickening and handling prepreg were obtained. In contrast, the crystalline resin composition of the present invention is heated and melted, and various additives, fillers, reinforcing agents, curing agents and the like are kneaded as necessary, and cooled to prepare a prepreg that can be handled in a predetermined size. Can be made. Thereafter, if the prepreg is hot-press molded, a molded product can be obtained by polymerizing and curing the crystalline resin composition after melting. That is, according to the present invention, it is not necessary to age for a long time, and the odor of the styrene monomer is not generated. Moreover, since it is not necessary to add a metal bond crosslinking agent, the transparent hardened | cured material of resin single is obtained.

  When used as a molded article, for example, a blender of a crystalline resin composition powder and a blend of glass fiber, filler, flame retardant, mold release agent, colorant, polymerization initiator, polymerization inhibitor, etc. If the mixture is uniformly mixed using a mold, the mixture is placed in a mold and heated and pressed, the crystalline resin is melted and polymerized and cured, and a desired molded product is obtained.

  In addition, since the crystalline resin composition of the present invention is a crystalline solid at room temperature, it can be made into a powder form and used as a powder paint. For example, the crystalline resin composition of the present invention is sprinkled on the surface of a heated substrate as a powder, spread over the entire surface of the substrate as a liquid, and further heated or irradiated with UV or EB. By doing so, a polymerization reaction can be advanced and a coating film can be formed.

Moreover, since the crystalline resin composition of the present invention can be transparent (including translucent), it can be used for transparent plates, colored plates, lenses, sealants and the like .

In the present invention, different types of R ₂ and R ₃ may be present .

( 2 ) The invention of claim 2
The gist is a resin material obtained by solidifying the crystalline resin composition according to claim 1 by a polymerization reaction.

The component constituting the crystalline resin composition of the present invention includes a site causing a polymerization reaction in the molecule (for example, an unsaturated bond contained in R ₂ or R ₃ , an unsaturated bond contained in a polymerizable compound having a hydroxyl group. Therefore, radical polymerization and ion polymerization based on these are possible, and normal temperature, heating, or ultraviolet rays (in some cases, high energy rays such as α rays, β rays, γ Curing with a beam, neutron beam, X-ray, electron beam) is possible.

The resin material of the present invention can be used as, for example, a decorative plate, a transparent plate, a colored plate, a lens, and a sealing material for various uses (for example, a casing of an electronic product).
( 3 ) The invention of claim 3
Hexamethylene diisocyanate having a compounding ratio of ½ mol with respect to 1 mol of the polymerizable compound having a hydroxyl group and the polymerizable compound having a hydroxyl group, which is allyl alcohol or ethylene glycol monoallyl ether, or 4,4 A first step of producing a crystalline monomer / oligomer having a urethane bond by addition reaction with '-diphenylmethane diisocyanate, a second step of mixing the crystalline monomer / oligomer produced in the first step and an unsaturated polyester. And a process for producing a crystalline resin composition that crystallizes and solidifies at room temperature.

The crystalline monomer / oligomer produced in the present invention has the same effects as the invention according to the first aspect.
In the production method of the present invention, the first step can be performed without using a solvent such as an organic solvent. For example, a method in which a compound having an isocyanate group is dropped into a polymerizable compound having a primary hydroxyl group and an unsaturated bond can be employed. At this time, the temperature of the reaction system is preferably maintained at a temperature (for example, in the range of 40 to 140 ° C.) at which the generated compound is maintained in a liquid state and the polymerization reaction between the crystalline monomer and the oligomer does not occur. And has a primary hydroxyl group, a polymerizable compound having an unsaturated bond, compounding ratio of the compound having an isocyanate group, the ratio of isocyanate groups to just disappear. The disappearance of the isocyanate group can be confirmed by a known analysis method (for example, FTIR).

The urethane condensation reaction in the first step can be performed without a catalyst, but di-n-butyltin dilaurate, amines and the like can also be used as a catalyst.
In the second step, for example, a crystalline monomer / oligomer and an unsaturated polyester (crystalline solid, liquid, or glassy at room temperature) are mixed, heated and melted, mixed uniformly, cooled to room temperature, and crystallized. There is a way to solidify. Alternatively, the crystalline monomer / oligomer and the unsaturated polyester component may be heated and melted, mixed together, and then cooled to room temperature to solidify the crystal.

  The blending ratio (weight ratio) of the crystalline monomer / oligomer and unsaturated polyester in the second step is preferably in the range of 95: 5 to 5:95, and more preferably in the range of 90:10 to 10:90. is there. In particular, in the case where the unsaturated polyester is an unsaturated polyester that becomes a crystalline solid at room temperature, a range of 5:95 to 80:20 is preferable.

The present invention will be described based on examples.
Example 1

(A) Synthesis of crystalline monomer / oligomer It is 116 g (2 mol) of allyl alcohol and a urethanization catalyst in a 2 liter separable flask equipped with a stirrer, thermometer, fraction condensing condenser (condenser), and dropping device. Di n-butyltin dilaurate 0.06g was added, it stirred, and it heated up at 70 degreeC. Next, 168 g (1 mol) of hexamethylene diisocyanate was added dropwise. At this time, the dropping speed was adjusted so that the internal temperature was 90 ° C. or lower. After completion of dropping, the internal temperature was maintained at 80 ° C., the reaction solution was sampled, and measured using FTIR. After confirming the disappearance of the absorption peak at 2275 cm ⁻¹ based on isocyanate (—N═C═O), the fraction condensation condenser was replaced with a fraction discharge condenser and unreacted under reduced pressure (20 mmHg) conditions. Allyl alcohol (bp. 97 ° C.) was distilled off. Here, in order to remove even a trace amount of allyl alcohol, 8 g of a trifunctional isocyanate oligomer (manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate HX) was added.

Thereafter, the reaction solution was transferred to a cooling vat and crystallized and solidified. Through the above steps, a crystalline monomer / oligomer represented by the formula ( 6 ) was synthesized.

(B) Physical Properties of Crystalline Monomer / Oligomer The melting point of the crystalline monomer / oligomer synthesized in (a) above is 74 ° C. (DTA analysis, temperature rising rate 10 ° C./min, endothermic peak tip temperature). It was a crystal. When heated to a temperature above the melting point (for example, 80 ° C.), it liquefies, but when cooled to room temperature, it became solid crystals again.

Further, the crystalline monomer / oligomer synthesized in the above (a) was stable even when left at room temperature in a state containing a curing agent.
(C) Synthesis of crystalline unsaturated polyester To a 3 L separable flask equipped with a stirrer, a distillation tube with a partial condenser, a cooling tube, a condensed water measuring graduated cylinder, a nitrogen gas introduction tube, and a thermometer, 929 g (8 Mol), 546 g (8.8 mol) of ethylene glycol, and 0.1 g of hydroquinone were charged, heating was started, and the mixture was stirred at a low speed so that no load was applied to the stirrer. When the fumaric acid was dissolved, the stirring speed was increased. When the temperature inside the flask reached 50 to 60 ° C., the inside was replaced with nitrogen gas. Condensed water began to come out at an internal temperature of 150 to 160 ° C. At this time, the degree of heating was controlled so that the top temperature of the partial condenser was 110 ° C. or lower. It heated up so that the inside of a flask might be 220-230 degreeC over about 4 hours. After reaching 220 ° C., nitrogen gas was injected to perform forced condensation (reaction temperature 220 to 230 ° C.). When the amount of distilled water reached 288 ml and the acid value was 30, it was cooled to room temperature, and a viscous unsaturated polyester solution was obtained. When left at room temperature for 3 days, a crystallized unsaturated polyester was obtained.
(D) Mixing of crystalline monomer / oligomer and unsaturated polyester 40 parts by weight of crystalline monomer / oligomer produced in (a) above and 60 parts by weight of crystalline unsaturated polyester produced in (c) above These were mixed in the state of crystal solidification, and then heated and melted at 100 ° C. for mixing. At this time, the liquid mixture had a low viscosity, and then cooled to room temperature to obtain a resin composition that immediately crystallized and solidified.
(E) Effect of crystalline resin composition The crystalline resin composition of Example 1 can be reduced in viscosity in a heated and melted state due to the dilution effect of the crystalline monomer / oligomer, and is easy to handle. It becomes. Therefore, it is not necessary to dilute with a styrene monomer or the like as in the prior art, and the problem of odor generation is eliminated. Further, the crystalline resin composition of Example 1 is crystallized in a short time when cooled (for example, cooled to room temperature) after being melted by heating. Therefore, if the crystalline resin composition of Example 1 is used as a molding material, a conventional aging step such as thickening by metal crosslinking is not necessary. Moreover, the fault that the crystalline solidification of crystalline polyester is slow can be eliminated.

In addition, a molding material can be manufactured as follows using the crystalline resin composition of the present Example 1. When 1% of dicumyl peroxide, which is a radical polymerization curing agent, is added to the resulting resin composition, put into a metal mold and thermoformed (temperature 130 ° C.), polymerization by unsaturated double bonds proceeds, Cured irreversibly. The cured product was transparent and had a hardness of 90D (ASTM, D2240).
(Example 2)

(A) Add 204 g (2 mol) of ethylene glycol monoallyl ether to a 2 liter separable flask equipped with a stirrer, thermometer, fraction condensing condenser (condenser), and dropping device, stir and raise to 70 ° C. Warm up. Next, 168 g (1 mol) of hexamethylene diisocyanate was added dropwise. At this time, the dropping speed was adjusted so that the internal temperature was 80 ° C. or lower. After completion of dropping, the internal temperature was maintained at 80 ° C., the reaction solution was sampled, and measured using FTIR. After confirming that the absorption peak at 2275 cm ⁻¹ based on isocyanate (—N═C═O) disappeared, the reaction solution was transferred to a cooling vat and crystallized and solidified. Through the above steps, a crystalline monomer / oligomer represented by the formula ( 7 ) was synthesized.

(B) Physical properties of crystalline monomer / oligomer The melting point of the crystalline monomer / oligomer synthesized in (a) above is 63 ° C. (DTA analysis, temperature rising rate 10 ° C./min, endothermic peak tip temperature). It was a solid. When heated to a temperature above the melting point (for example, 80 ° C.), it liquefies, but when cooled to room temperature, it became solid again.

Furthermore, the crystalline monomer / oligomer synthesized in the above (a) was stable even when allowed to stand at room temperature in a state containing a curing agent.
(C) Synthesis of crystalline unsaturated polyester The same crystalline unsaturated polyester as in Example 1 was synthesized.
(D) Mixing of crystalline monomer / oligomer and unsaturated polyester 40 parts by weight of crystalline monomer / oligomer produced in (a) above and 60 parts by weight of crystalline unsaturated polyester produced in (c) above These were mixed in the state of crystal solidification, and then heated and melted at 100 ° C. for mixing. At this time, the mixed solution had a low viscosity. Then, when it cooled to normal temperature, the resin composition which solidified immediately was obtained.

Add 1% of dicumyl peroxide, a radical polymerization curing agent, to the above mixed solution, put it in a metal mold, and heat-mold (for example, at a temperature of 130 ° C.). Cured to. The cured product was transparent and the hardness was 90D (ASTM, D2240).
(E) Effect exhibited by crystalline resin composition The crystalline resin composition of Example 2 exhibits the same effects as in Example 1.
( Reference Example 3)

Basically, in the same manner as in Example 1, a crystalline resin composition containing a crystalline monomer / oligomer and an unsaturated polyester was produced. However, in Reference Example 3, a crystalline monomer / oligomer produced as follows was used.
(Synthesis of crystalline monomers and oligomers)
Diethylene glycol monovinyl ether 264 g (2 mol) and di-n-butyltin dilaurate 0.13 g as a urethanization catalyst were added to a 2 liter separable flask equipped with a stirrer, thermometer, fraction condensing condenser (condenser) and dropping device. The mixture was stirred and heated to 85 ° C. Next, 168 g (1 mol) of hexamethylene diisocyanate was added dropwise. At this time, the dropping speed was adjusted so that the internal temperature was 90 ° C. or lower. After completion of dropping, the internal temperature was maintained at 85 ° C., the reaction solution was sampled, and measured using FTIR. After confirming that the absorption peak at 2275 cm ⁻¹ based on isocyanate (—N═C═O) disappeared, the reaction solution was transferred to a cooling vat and crystallized and solidified. Through the above steps, a crystalline monomer / oligomer represented by the formula ( 8 ) was synthesized.

The melting point of the crystalline monomer / oligomer was 79 ° C. (DTA analysis, temperature rising rate 10 ° C./min, endothermic peak tip temperature), and was a crystalline solid at room temperature. The temperature above the melting point (eg, the crystalline monomer / oligomer described above was stable even when allowed to stand at room temperature in a state containing a curing agent.
( Reference Example 4)

Basically, in the same manner as in Example 1, a crystalline resin composition containing a crystalline monomer / oligomer and an unsaturated polyester was produced. However, in Reference Example 4, a crystalline monomer / oligomer produced as follows was used.
(Synthesis of crystalline monomers and oligomers)
In a 2 liter separable flask equipped with a stirrer, a thermometer, a fraction condensing condenser (condenser), and a dropping device, 260 g (2 mol) of 2-hydroxyethyl methacrylate and di-n-butyltin dilaurate 0 as a urethanization catalyst .13 g was added, stirred and heated to 70 ° C. Next, 168 g (1 mol) of hexamethylene diisocyanate was added dropwise. At this time, the dropping speed was adjusted so that the internal temperature was 90 ° C. or lower. After completion of dropping, the internal temperature was maintained at 80 ° C., the reaction solution was sampled, and measured using FTIR. After confirming that the absorption peak at 2275 cm ⁻¹ based on the isocyanate group (—N═C═O) disappeared, the reaction solution was transferred to a cooling bat and crystallized and solidified. Through the above steps, a crystalline monomer / oligomer represented by the formula ( 9 ) was synthesized.

  The melting point of the crystalline monomer / oligomer was 78 ° C. (DTA analysis, temperature rising rate 10 ° C./min, endothermic peak tip temperature), and it was a crystalline solid at room temperature. When heated to a temperature above the melting point (for example, 80 ° C.), it liquefies, but when cooled to room temperature, it became solid again.

The crystalline monomer / oligomer described above was stable even when left at room temperature for a long time in a state containing a curing agent.
( Reference Example 5)

Basically, in the same manner as in Example 1, a crystalline resin composition containing a crystalline monomer / oligomer and an unsaturated polyester was produced. However, in Reference Example 5, the crystalline monomer / oligomer produced as follows was used.
(Synthesis of crystalline monomers and oligomers)
In a 2 liter separable flask equipped with a stirrer, thermometer, fraction condensing condenser (condenser) and dropping device, 232 g (2 mol) of 2-hydroxyethyl acrylate and di-n-butyltin dilaurate as a urethanization catalyst were added. 12g was added, it stirred, and it heated up at 70 degreeC. Next, 168 g (1 mol) of hexamethylene diisocyanate was added dropwise. At this time, the dropping speed was adjusted so that the internal temperature was 90 ° C. or lower. After completion of dropping, the internal temperature was maintained at 80 ° C., the reaction solution was sampled, and measured using FTIR. After confirming that the absorption peak at 2275 cm ⁻¹ based on isocyanate (—N═C═O) disappeared, the reaction solution was transferred to a cooling vat and crystallized and solidified. Through the above steps, a crystalline monomer / oligomer represented by the formula ( 10 ) was synthesized.

  The melting point of the crystalline monomer / oligomer was 80 ° C. (DTA analysis, temperature rising rate 10 ° C./min, endothermic peak tip temperature), and was a crystalline solid at room temperature. When heated to a temperature above the melting point (for example, 85 ° C.), it liquefies, but when cooled to room temperature, it became solid again.

The crystalline monomer / oligomer described above was stable even when allowed to stand at room temperature in a state containing a curing agent.
(Example 6)

A mixture of the crystalline monomer / oligomer obtained in Example 2 and an unsaturated polyester (hereinafter referred to as a resin composition) was heated to 100 to 110 ° C. to obtain a liquid. To 100 parts by weight of this resin composition, 100 parts by weight of aluminum hydroxide (H-320ST methacrylic silane treated product, Showa Denko) and 5 parts by weight of color pigment were added and mixed uniformly. Next, the mixture was cooled to 90 ° C., and 0.5 parts by weight of dicumyl peroxide was added and mixed. An 80 g / m ² glass fiber nonwoven fabric was coated and impregnated with the above mixed solution under the condition of 960 g / m ² , and then cooled to room temperature to obtain a prepreg sheet. Six prepreg sheets were placed in a mold and press-molded under the conditions of 140 ° C. and 70 Kg / m ² . As a result, a natural stone-like molded plate having a thickness of 3 mm was obtained. The hardness of the molded plate was 93D (ASTM D2240), and it did not break even when dropped from a height of 2 m onto the concrete ground.
(Example 7)

  Basically, in the same manner as in Example 1, a crystalline resin composition containing a crystalline monomer / oligomer and an unsaturated polyester was produced. However, in Example 7, a crystalline monomer / oligomer obtained by reacting raw material 1 and raw material 2 shown in Table 1 was used.

  The production method of the crystalline monomer / oligomer in Example 7 is basically the same as in Example 1, except that raw material 1 is used instead of allyl alcohol, and raw material 2 is used instead of hexamethylene diisocyanate. Using. The amounts of raw material 1 and raw material 2 were 2 mol and 1 mol, respectively. The temperature during the reaction was adjusted according to the substance so that it did not solidify during the reaction and was not polymerized. As the catalyst, di-n-butyltin dilaurate was used when the raw material 2 was HDI, and was not used when the raw material 2 was 4,4′MDI. Only when allyl alcohol was used as the raw material 1, a small amount of trifunctional isocyanate was finally added in order to remove unreacted allyl alcohol. The melting point did not change whether or not trifunctional isocyanate was added. Table 1 also shows the melting point of the produced crystalline monomer / oligomer.

Needless to say, the present invention is not limited to the above-described embodiments, and can be implemented in various modes without departing from the scope of the present invention.
For example, the crystalline unsaturated polyester in the above examples is described in JP-A No. 2003-183368, JP-A No. 49-131289, JP-A No. 50-102688, and JP-A No. 60-49221. It may be. That is, the crystalline unsaturated polyester may be produced as follows.
(Another method for producing crystalline unsaturated polyester)
A reactor equipped with a stirrer, a distillation tube, a nitrogen gas inlet tube and a thermometer is charged with 1.4-butanediol, dimethyl terephthalate and optionally other dimethyl esters and glycols. As a catalyst, 0.02 mol% of titanic acid tetra-n-butoxide and 0.03 mol% of antimony trioxide are charged with respect to all acid components. Transesterification is carried out by raising the internal temperature to 140 ° C. and further raising the temperature to 200 ° C. over 1.5 hours and distilling methanol. Next, the internal temperature is lowered to 160 ° C., 150 ppm of fumaric acid and hydroquinone are added, the internal temperature is increased to 155 ° C. while flowing nitrogen at 300 ml / min, the internal temperature is increased to 160 ° C. over 2.0 hours, and further 2.5 The temperature is raised to 210 ° C. over time, and the reaction is continued at the same temperature for 5.5 hours. In the latter 4.0 hours, the nitrogen flow rate is increased to 680 ml / min. The produced polymer is discharged, cooled and crystallized, and then pulverized using a Henschel mixer to obtain an unsaturated polyester.

  Here, the blending amounts of 1.4-butanediol, dimethyl terephthalate, other dimethyl esters, other glycols, and phthalic acid can be as shown in Table 2.

  In Table 1, DMSA is dimethyl sebacate, DMI is dimethyl isophthalate, and BPE is a bisphenol A ethylene oxide 2-mole adduct. Moreover, the unit of the compounding quantity in Table 1 is a weight part.

Claims (3)

A crystalline resin composition comprising a crystalline monomer / oligomer (A) represented by the formula (1) and an unsaturated polyester (B) and crystallizing at room temperature.
However, R < ₁ > is group represented by Formula (2) or Formula (3), and R < ₂ >, R < ₃ > is group represented by Formula (4) or Formula (5).

A resin material obtained by solidifying the crystalline resin composition according to claim 1 by a polymerization reaction. Hexamethylene diisocyanate having a compounding ratio of ½ mol with respect to 1 mol of the polymerizable compound having a hydroxyl group and the polymerizable compound having a hydroxyl group, which is allyl alcohol or ethylene glycol monoallyl ether, or 4,4 A first step of producing a crystalline monomer / oligomer having a urethane bond by addition-reacting with '-diphenylmethane diisocyanate;
A second step of mixing the crystalline monomer / oligomer produced in the first step and the unsaturated polyester;
A process for producing a crystalline resin composition that crystallizes at room temperature.