JP3377592B2 - Modifier for unsaturated urethane resin for curing molding, unsaturated urethane resin composition for curing molding containing the same, and curing molding method therefor - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modifier for an unsaturated urethane resin for curing and molding (hereinafter referred to simply as a modifier), and an unsaturated urethane resin composition for curing and molding containing the same (hereinafter referred to simply as a composition). ) And its curing molding method. Unsaturated polyester resins, unsaturated urethane resins and the like are known as radical curable resins, and cured moldings obtained from these radical curable resins are widely used.
These cured moldings are required to be free from defects such as warpage, cracks, and unevenness due to shrinkage during curing molding, and have transparency in relation to applications and curing molding methods. Is required. The present invention relates to a modifier, a composition, and a method for curing and molding the same, which meet such demands.

[0002]

2. Description of the Related Art Conventionally, as means for preventing shrinkage of a radical-curable resin during curing and molding, 1) a radical-curable resin is made to contain a soluble thermoplastic polymer and the thermoplastic polymer is cured and molded. Means for finely phase-separating micro-domains to form micro-domains, and using thermal expansion of the phase-separated thermoplastic resin to prevent shrinkage during curing molding {2
6th Annual Technical Conference SPI 12F
(1971)}, 2) means for containing inorganic fine particles,
3) Means for containing fine particles of a crosslinked polymer insoluble in a radical-curable resin, for example, an example of containing fine particles of a styrene-divinylbenzene copolymerized crosslinked polymer in an unsaturated polyester resin (JP-A-48-81984) Etc.

However, in the conventional means of 1), the curing temperature and the curing speed have a great influence on the phase separation of the thermoplastic polymer to form the microdomains, and it is extremely complicated to set an appropriate condition. In addition, there is a drawback that the transparency of the obtained cured molded article is decreased as the shrinkage at the time of curing molding is prevented. Further, the conventional means of 2) has a drawback that the content of the inorganic fine particles is generally required to be increased in order to prevent shrinkage at the time of curing and molding, and thus the transparency of the cured molding obtained is remarkably impaired. And, the conventional means of 3) has a drawback that the transparency of the obtained cured molded article is not improved even though the shrinkage at the time of curing molding can be prevented.

[0004]

The problem to be solved by the present invention is that the conventional means cannot prevent shrinkage at the time of curing molding and improve the transparency of the obtained cured molded product.

[0005]

However, the present inventors have
Regarding the curing and molding of unsaturated urethane resin among the radical curable resins, as a result of earnest research to solve the above problems, it is correct and preferable to use crosslinked polymer particles obtained by radically polymerizing a specific unsaturated urethane resin. I found that.

That is, the present invention relates to a modifier characterized by comprising crosslinked polymer particles obtained by radically polymerizing the following unsaturated urethane resin, a composition containing the same and a method for curing and molding the same.

Unsaturated urethane resin: One or more unsaturated urethanes selected from the unsaturated urethanes represented by the following formula 1 and the unsaturated urethanes represented by the following formula 2; An unsaturated urethane resin in which the polymerizable (meth) acrylic acid ester is in a ratio of the unsaturated urethane / the (meth) acrylic acid ester = 80/20 to 20/80 (weight ratio).

[0008]

[Formula 1]

[0009]

[Formula 2]

[In the formulas 1 and 2, X ¹ , X ² are residues Y ¹ , Y ² , Y ^{3 obtained} by removing an isocyanate group from a polyisocyanate selected from diisocyanates and triisocyanates: Residue Y ⁴ removed: Residues R ¹ , R ³ , R ⁵ , R ⁷ , R ⁸ : H or obtained by removing a hydroxyl group from a divalent or trivalent polyol selected from polyhydric alcohols, polyether polyols and polyester polyols _{^{CH 3 R 2, R 4,}} R 6: aliphatic hydrocarbon group j of 5 to 21 carbon atoms, k, m, n: a 1 or 2, and satisfies the j + k = 2 or 3, also m + n = Those satisfying 2 or 3 p, q: 0 to 2 and satisfying p + q = 1 or 2]

The unsaturated urethane represented by the formula 1 is 1)
(Meth) acrylic acid / long-chain fatty acid mixed ester monool (hereinafter simply referred to as mixed ester monool), a urethane reaction product of diisocyanate, and 2) a mixed ester monool and triisocyanate urethane reaction product. Include.

The mixed ester monool is a partial ester which is synthesized from (meth) acrylic acid, a long-chain fatty acid having 6 to 22 carbon atoms and a trivalent alcohol and has one free hydroxyl group in the molecule.

Examples of the trihydric alcohol used to synthesize the mixed ester monool include glycerin, trimethylolethane, trimethylolpropane, 1,2,6-
Hexanetriol and the like can be mentioned.

The long chain fatty acid used for synthesizing the mixed ester monool is a saturated or unsaturated fatty acid having 6 to 22 carbon atoms and having a straight chain or a branched chain. Such long-chain fatty acids include 1) hexanoic acid, octanoic acid,
Linear saturated fatty acids such as dodecanoic acid and stearic acid 2)
Examples thereof include branched chain saturated fatty acids such as isooctanoic acid, isopalmitic acid and isostearic acid, 3) unsaturated fatty acids such as oleic acid and elaidic acid, and mixtures thereof.

The present invention does not particularly limit the method for synthesizing the mixed ester monool. Examples of the synthetic method include a direct esterification reaction between a trihydric alcohol, (meth) acrylic acid and a long chain fatty acid, and a long chain. Examples of the ring-opening addition reaction of a fatty acid glycidyl ester and (meth) acrylic acid, a ring-opening addition reaction of a glycidyl (meth) acrylate and a long-chain fatty acid, and the like can be mentioned. 1 mol of (meth) acrylic acid and 1 mol of long-chain fatty acid are ester-bonded with 1 mol of trivalent alcohol.

The mixed ester monools thus synthesized include 1) glycerin monomethacrylate monooctanoate, trimethylolpropane monoacrylate monoisononanoate, and 5-methyl-1,2,4.
-Heptanetriol monomethacrylate monooleate, 1,2,6-hexanetriol monomethacrylate mono-2-ethylhexoate and the like,
Glycerin mono (meth) acrylic acid / mono long-chain fatty acid mixed ester monool can be advantageously used.

The unsaturated urethane represented by the formula 2 is 1) a 1: 1: 1 (molar ratio) urethanization reaction product of a mixed ester monool, a (meth) acrylic ester monool and a diisocyanate, and 2) a mixture. The urethanization reaction product of ester monool, (meth) acrylic ester monool, and triisocyanate in a ratio of 1: 2: 1 (molar ratio) or 2: 1: 1 (molar ratio) is included.

The (meth) acrylic ester monool is
1) Partial ester obtained from 1 mol of (meth) acrylic acid and 1 mol of diol, 2) Partial ester obtained from 2 mol of (meth) acrylic acid and 1 mol of triol are included, each of which is 1 in the molecule. It has a free hydroxyl group.

The diol or triol used to synthesize the (meth) acrylic ester monool is 1).
Di- or trihydric alcohol, 2) polyether diol,
Polyether triol, 3) polyester diol,
Examples include polyester triols.

Examples of the (meth) acrylic ester monool include 1) 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate and 1,6-hexanediol monoacrylate.
Monohydric alcohol mono (meth) acrylate, 2) glycerin diacrylate, glycerin dimethacrylate, trimethylolpropane dimethacrylate, 5-methyl-1,2,4-heptanetriol dimethacrylate, 1,2,6-hexanetriol Di (meth) acrylate of trihydric alcohol such as dimethacrylate,
3) Mono (meth) acrylates of polyether diols such as polyethylene glycol monoacrylate and polypropylene glycol monomethacrylate, 4) ethylene glycol monoglyceryl ether dimethacrylate, (poly) ethoxylated trimethylolpropane dimethacrylate, (poly) propoxyl (Poly) ether triol di (meth) acrylates such as trimethylolpropane dimethacrylate, 5) Polycaprolactone diol monomethacrylate, polyneopentyl adipate diol monoacrylate, and other polyester diol mono (meth) acrylates, 6) Polycaprolactone triol diacrylate starting from trihydric alcohol Polycaprolactone to starting trihydric alcohol Such as all-di-methacrylate, di (meth) acrylate of polyester triol.

The diol or triol used for synthesizing the (meth) acrylic ester monool has a molecular weight of 20 per hydroxyl group contained in the molecule.
Those of 0 or less can be advantageously used, but those of 150 or less can be particularly advantageously used.

The polyisocyanates to be reacted with the mixed ester monools and (meth) acrylic ester monools exemplified above include 1) various tolylene diisocyanates, methylene-bis- (4-phenylisocyanate) and other aromatic compounds. Diisocyanate, 2) Aliphatic diisocyanate or alicyclic diisocyanate such as hexamethylene diisocyanate, methylene-bis- (4-cyclohexyl isocyanate), 3) 4-isocyanatomethyl-1-isocyanato-1-methyl-cyclohexane, 5-isocyanate Natomethyl-1-isocyanato-1,
Aliphatic / alicyclic diisocyanates such as 1-dimethyl-5-methyl-cyclohexane (isophorone diisocyanate), and aromatic polyisocyanates such as 4) polymethylene polyphenyl polyisocyanate (NCO group average 3).

In the unsaturated urethane represented by the formula 1,
The same mixed ester monool can be used, or different ones can be used. Also in the unsaturated urethane represented by the formula 2, triisocyanate / mixed ester monool / (meth) acrylic ester monool = 1/2/1 (molar ratio) or 1/1 /
When reacting at 2 (molar ratio), different mixed ester monools or (meth) acrylic ester monools can be used.

When diisocyanate is used as the polyisocyanate and different mixed ester monools are used as the mixed ester monool, the unsaturated urethane represented by the formula 1 becomes an asymmetric unsaturated urethane. When diisocyanate is used as the polyisocyanate, the unsaturated urethane represented by the formula 2 also becomes an asymmetric unsaturated urethane. As the diisocyanate used for synthesizing the asymmetric unsaturated urethane, those having an isocyanate group that is affected by a sterically hindering substituent and an isocyanate group that is not affected by the same, or an aliphatic hydrocarbon It is preferable to use diisocyanates having isocyanate groups having mutually different reactivities, such as those having an isocyanate group bonded to a group and an isocyanate group bonded to an aromatic hydrocarbon group. Diisocyanate, isophorone diisocyanate, 4
-Isocyanatomethyl-1-isocyanato-1-methyl-cyclohexane and the like can be mentioned.

The present invention is not particularly limited to the method for synthesizing unsaturated urethane, and a known method such as the method described in JP-A-4-53809 can be applied to the synthesis thereof, but diisocyanate is used. In order to synthesize an asymmetric unsaturated urethane obtained by using, 1 mol of the mixed ester monool and 1 mol of the above-mentioned diisocyanate having an isocyanate group having different reactivity are previously reacted to obtain an unsaturated urethane monoisocyanate. A method of reacting a mixed ester monool or a (meth) acrylic ester monool different from is preferred.

Examples of the (meth) acrylic acid ester used in combination with the unsaturated urethane represented by the formula 1 or 2 are 1) butyl acrylate, alkyl acrylate such as 2-ethylhexyl acrylate, 2) methyl methacrylate, ethyl methacrylate, isobutyl methacrylate. Such as 3) ethylene glycol diacrylate, neopentyl glycol diacrylate, dicyclopentene dimethylene diacrylate, etc., diacrylate of dihydric alcohol, 4) 1,4-butanediol dimethacrylate, 1,6-hexanediol Dimethacrylate of dihydric alcohol such as dimethacrylate,
5) Trihydric alcohol triacrylates such as glycerin triacrylate and trimethylolpropane triacrylate; 6) Trihydric alcohol trimethacrylates such as glycerin trimethacrylate and trimethylolethane trimethacrylate; 7) Trimethylolpropane diacrylate. Mixed (meth) acrylates of trihydric alcohols such as monomethacrylate and glycerin monoacrylate / dimethacrylate, 8) pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate
Tetra (meth) acrylate of tetrahydric alcohol such as dimethacrylate, 9) Polyether polyol obtained by adding alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide to the above-mentioned dihydric or tetrahydric alcohol, acrylic acid, methacrylic acid A polyether polyol poly (meth) acrylate obtained from these mixed acids, 10) a polyester polyol obtained by adding an aliphatic lactone such as caprolactone or butyrolactone to the above-mentioned dihydric to tetrahydric alcohol, acrylic acid, methacrylic acid, Polyester polyol poly (meth) acrylate obtained from these mixed acids, 1
1) Examples include alkoxylated bisphenol di (meth) acrylates such as 2,2-bis (acryloxyethoxyphenyl) propane and bis (acryloxypolyethoxyphenyl) methane.

In the unsaturated urethane resin used in the present invention, the ratio of the unsaturated urethane and the (meth) acrylic acid ester copolymerizable with the unsaturated urethane is such that the unsaturated urethane / the (meth) acrylic acid ester. = 80/20 ~
20/80 (weight ratio), preferably 30/70 to 7
The ratio is 0/30 (weight ratio). The ratio of both is 20/80
Less than (weight ratio) or conversely 80/20 (weight ratio)
If it exceeds, the degree of the desired effect as a modifier of the crosslinked polymer particles obtained from such unsaturated urethane resin will be insufficient.

The modifier of the present invention comprises crosslinked polymer particles obtained by radically polymerizing the unsaturated urethane resin as described above. The unsaturated urethane and (meth) acrylic acid ester to be used for radical polymerization of the crosslinked polymer particles can be arbitrarily selected from the above-mentioned ones and can be used. In order to develop the desired effect better, particularly in order to achieve the desired effect better in the curing molding by photopolymerization described later, as unsaturated urethane, among R ¹ and R ³ of the formula 1, From the unsaturated urethane of formula 1 when at least one is H and the unsaturated urethane of formula 2 when at least one of R ⁵ , R ⁷ and R ⁸ of formula 2 is H. It is preferable to use one or two or more selected. Moreover, as the (meth) acrylic acid ester used in combination with these unsaturated urethanes, any one or two or more polyols selected from alcohols, polyether polyols, polyester polyols and alkoxylated bisphenols each having 2 to 4 valences can be used. It is preferable to use an acrylic ester or a mixed (meth) acrylate of the polyol and acrylic acid and methacrylic acid.

As a method for obtaining a crosslinked polymer particle by radical polymerization of an unsaturated urethane resin, 1) a crosslinked polymer obtained by radical polymerization of an unsaturated urethane resin by a known solution polymerization method or bulk polymerization method is obtained. Is pulverized by known physical means, and further classified. 2) After radical polymerization of an unsaturated urethane resin by a known suspension polymerization method or emulsion polymerization method, a crosslinked polymer particle is prepared from the reaction system by an arbitrary method. And the like. A known radical polymerization initiator is used in any radical polymerization.

Although the present invention does not particularly limit the shape and size of the crosslinked polymer particles, the crosslinked polymer particles are preferably particles having an average particle diameter of 0.1 to 100 μm, and an average particle diameter of 0.1. Spherical particles of 1 to 30 μm are particularly preferred. In order to obtain crosslinked polymer particles having such a particle shape and particle size, it is preferable to radically polymerize the unsaturated urethane resin by a suspension polymerization method or an emulsion polymerization method. Since the crosslinked polymer particles used as the modifier of the present invention have a highly crosslinked structure, they are not dissolved or swollen by the unsaturated urethane resin in the composition of the present invention as described below, It prevents shrinkage of the composition during curing and molding, and improves the transparency of the cured molding obtained at the same time.

The composition of the present invention comprises an unsaturated urethane resin 1
It contains 50 to 300 parts by weight, and preferably 100 to 250 parts by weight, of the modifier composed of the cross-linked polymer particles as described above with respect to 00 parts by weight. If the content ratio of the modifier to 100 parts by weight of the unsaturated urethane resin is less than 50 parts by weight, and conversely if it exceeds 300 parts by weight, the desired effect is obtained when such a composition is cured and molded. The degree of expression is insufficient.

The present invention does not specifically limit the unsaturated urethane used in combination with the modifying agent of the present invention, but as the unsaturated urethane resin, the following unsaturated urethane resins are preferably used. Unsaturated urethane resin: One or more kinds of unsaturated urethane selected from the unsaturated urethane represented by the following formula 3 and the unsaturated urethane represented by the following formula 4, and copolymerizable with the unsaturated urethane (Meta)
Unsaturated urethane resin which acrylic ester consists of the ratio of this unsaturated urethane / this (meth) acrylic acid ester = 80 / 20-20 / 80 (weight ratio).

[0033]

[Formula 3]

[0034]

[Formula 4]

[In formulas 3 and 4, X ³ , X ⁴ are residues Y ⁵ , Y ⁶ , Y ^{7 obtained} by removing an isocyanate group from a polyisocyanate selected from diisocyanates and triisocyanates: Residues Y ⁸ removed: residues R ⁹ , R ¹¹ , R ¹³ , R ¹⁵ , R ¹⁶ : H or a hydroxyl group removed from a divalent or trivalent polyol selected from polyhydric alcohols, polyether polyols and polyester polyols _{^{CH 3 R 10, R 12,}} R 14: aliphatic hydrocarbon group r of 5 to 21 carbon atoms, s, t, u: a 1 or 2 and satisfy r + s = 2 or 3, also t + u = Those satisfying 2 or 3 v, w: 0 to 2 and satisfying v + w = 1 or 2]

In the composition of the present invention, the formula 3 representing the unsaturated urethane constituting the unsaturated urethane resin is the unsaturated urethane constituting the unsaturated urethane resin used for the radical polymerization of the crosslinked polymer particles as the modifier. Equation 1 corresponds to Equation 1, similarly Equation 4 corresponds to Equation 2, and Equation 1 and Equation 2
Since the above is as described above, the description of the formulas 3 and 4 will be omitted here. The (meth) acrylic acid ester that constitutes the unsaturated urethane resin is the same as the (meth) acrylic acid ester that constitutes the unsaturated urethane resin used for the radical polymerization of the crosslinked polymer particles that is the modifier. Since it is as described above, the description of the (meth) acrylic acid ester is omitted here.

In the composition of the present invention, as the unsaturated urethane and (meth) acrylic acid ester constituting the unsaturated urethane resin, the unsaturated urethane resin to be used for the radical polymerization of the crosslinked polymer particles as the modifier is described above. It can be used by arbitrarily selecting from among the
In order to better develop the desired effect in the composition to be prepared, in particular, in order to better develop the desired effect in the curing and molding by photopolymerization described later, as unsaturated urethane, R of formula 3 is used. An unsaturated urethane of formula 3 when at least one of ⁹ and R ¹¹ is H, and at least one of R ¹³ , R ¹⁵ and R ¹⁶ of formula 4 is H
It is preferable to use one kind or two or more kinds selected from the unsaturated urethane represented by the formula 4 in the case of Moreover, as the (meth) acrylic acid ester used in combination with these unsaturated urethanes, any one or two or more polyols selected from alcohols, polyether polyols, polyester polyols and alkoxylated bisphenols each having 2 to 4 valences can be used. It is preferable to use an acrylic ester or a mixed (meth) acrylate of the polyol and acrylic acid and methacrylic acid.

In a similar sense, when the unsaturated urethane constituting the unsaturated urethane resin of the composition of the present invention is the unsaturated urethane represented by the formula 3, the unsaturated urethane forming the modifier is formed. The unsaturated urethane constituting the urethane resin is preferably the unsaturated urethane represented by the formula 1, and the unsaturated urethane constituting the unsaturated urethane resin of the composition of the present invention is the unsaturated urethane represented by the formula 4. In some cases, the unsaturated urethane constituting the unsaturated urethane resin that will form the modifier is preferably the unsaturated urethane represented by Formula 2.

The composition of the present invention can be cured and molded by radical polymerization using a radical polymerization initiator at room temperature or under heating, but energy rays such as ultraviolet rays and electron beams are used in the presence of a photopolymerization initiator. It is particularly effective when curing and molding by photopolymerization. A known method using a photopolymerization initiator and energy rays can be applied to the curing and molding by photopolymerization. Examples of the photopolymerization initiator include 1) carbonyl compounds such as benzoin, α-methylbenzoin, anthraquinone, chloranthraquinone and acetophenone, 2) sulfur compounds such as diphenylsulfide, diphenyldisulfide and dithiodicarbamate, and 3) α-chloromethylnaphthalene. , And polycyclic aromatic compounds such as anthracene. The present invention does not particularly limit the proportion of the photopolymerization initiator used in the composition of the present invention, but usually 0.1 part of the photopolymerization initiator is added to 100 parts by weight of the unsaturated urethane resin in the composition. It is used in a ratio of 10 to 10 parts by weight. A photosensitizer such as n-butylamine, triethanolamine, N, N-dimethylaminobenzenesulfonic acid diallylamide, or N, N-dimethylaminoethyl methacrylate can be used together with the photopolymerization initiator. Examples of energy rays include visible rays, ultraviolet rays, and electron rays, but ultraviolet rays can be advantageously applied.

The composition of the present invention is particularly effective in the case of curing and molding by photopolymerization. Above all, it is most effective to apply the composition of the present invention to optical stereolithography by photopolymerization. Thus, a cured molded product having excellent dimensional accuracy, appearance and transparency can be obtained. In order to apply the composition of the present invention to such optical three-dimensional modeling, the composition of the present invention together with the unsaturated urethane constituting the unsaturated urethane resin forming the modifier of the present invention and the modifier. It is preferable that both of the unsaturated urethane constituting the unsaturated urethane resin forming a have an acryloyl group and a methacryloyl group as a polymerizable group in the molecule, among them, as described above,
When the unsaturated urethane represented by the formula 1 is used as the modifier, it is preferable to use the unsaturated urethane represented by the formula 3 in the composition using the modifier, and the unsaturated urethane represented by the formula 2 is used as the modifier. When unsaturated urethane is used, it is preferable to use the unsaturated urethane represented by the formula 4 in the composition using the modifier. Further, as the (meth) acrylic acid ester used in combination with these unsaturated urethanes, both are 2
A tetravalent acrylate ester of one or more polyols selected from alcohols, polyether polyols, polyester polyols and alkoxylated bisphenols, or a mixed (meth) acrylate of the polyol with acrylic acid and methacrylic acid. It is preferably used.

Various methods are known as optical three-dimensional molding methods (Japanese Patent Laid-Open Nos. 56-144478 and 60-60).
247514, JP-A-1-204915, JP-A-3-4
1126), for example, an operation of forming a cured layer first, and then supplying an uncured composition on the cured layer, and irradiating the composition with an energy ray to form a next cured layer. Is repeated to form a desired cured molded article, and post-curing is further performed if necessary.

[0042]

【Example】

Test Category 1 (Preliminary Synthesis) Preliminary Synthesis Examples 1 to 3 shown below were performed. In each preliminary synthesis example, parts are parts by weight. Preliminary Synthesis Example 1 144 parts (1.0 mol) of octanoic acid and 2 parts of triethylamine as a catalyst were placed in a reaction vessel, kept at 70 ° C. and stirred, and 128 parts of glycidyl acrylate (1.0 part).
Mol) was added dropwise over 30 minutes. After that, the reaction system is changed to 70
The synthesis was completed by holding at 5 ° C for 5 hours. The oxirane oxygen content of the reaction product was quantified, but was hardly detected. The reaction product obtained here was 272 parts of glycerin monoacrylate monooctanoate, and had an acid value of 0.9, a hydroxyl value of 205, and a saponification value of 412.

Preliminary Synthesis Example 2 Synthesis was carried out in the same manner as in Preliminary Synthesis Example 1 using 144 parts (1.0 mol) of octanoic acid, 2 parts of triethylamine and 142 parts (1.0 mol) of glycidyl methacrylate.
The reaction product obtained here was 286 parts of glycerin monomethacrylate monooctanoate, and had an acid value of 0.7, a hydroxyl value of 198, and a saponification value of 390.

Preliminary Synthesis Example 3 Synthesis was carried out in the same manner as in Preliminary Synthesis Example 1 using 256 parts (1.0 mol) of isopalmitic acid, 3 parts of triethylamine and 142 parts (1.0 mol) of glycidyl methacrylate. The reaction product obtained here was 398 parts of glycerin monomethacrylate monoisopalmitate, and had an acid value of 1.1, a hydroxyl value of 140, and a saponification value of 281.

Test Category 2 (Synthesis of Unsaturated Urethane and Preparation of Unsaturated Urethane Resin) Synthesis of unsaturated urethane and preparation of unsaturated urethane resin shown below were carried out. The types and amounts of the raw materials used in the synthesis are summarized in Tables 1 and 2. In the synthesis of each unsaturated urethane and the preparation of the unsaturated urethane resin, parts are parts by weight and% is% by weight. -Synthesis of unsaturated urethane A-1 and preparation of unsaturated urethane resin a-1 87 parts (0.5 mol) of 2,4-tolylene diisocyanate, 100 parts of dry toluene and 0.5 parts of di-n-butyltin dilaurate. Parts in a reaction vessel, kept at 50 ° C. and stirred, and 143 parts (0.5 mol) of glycerin monomethacrylate monooctanoate obtained in Pre-synthesis Example 2
Was added dropwise over 30 minutes. During this period, the reaction temperature is 50 to 6
It was kept at 0 ° C. Then, the reaction was continued at 50 to 55 ° C., and the reaction was terminated when the residual amount of isocyanate groups in the reaction product became 1/2 of the theoretical amount calculated from the amount of diisocyanate used in the reaction. The reaction product obtained here is 2,
It is an unsaturated urethane monoisocyanate in which 4-tolylene diisocyanate and glycerin monomethacrylate monooctanoate are bonded at a 1/1 (molar ratio). Next, this reaction product was maintained at 60 ° C. and stirred, and further 136 parts (0.5 mol) of glycerin monoacrylate / monooctanoate obtained in Preliminary Synthesis Example 1 was added dropwise over 30 minutes. At this time, reaction heat is generated, but the reaction temperature is 60 to 70 ° C.
Kept at. Then, it hold | maintained at 70 degreeC for 2 hours, and unsaturated urethane A-1 was synthesize | combined. Furthermore, 366 parts of polyoxypropylene glycol (molecular weight 200) diacrylate was added and dissolved, and toluene was distilled off under reduced pressure to obtain 50% unsaturated urethane A-1 and polyoxypropylene glycol (molecular weight 200) diacrylate. An unsaturated urethane resin a-1 containing 50% was prepared.

Synthesis of unsaturated urethane A-2 and preparation of unsaturated urethane resin a-2 Synthesis of unsaturated urethane A-1 and unsaturated urethane resin a
In the same manner as in the preparation of -1, unsaturated urethane A-2 was synthesized and unsaturated urethane resin a-2 was prepared.

Synthesis of Unsaturated Urethane A-3 and Preparation of Unsaturated Urethane Resin a-3 286 parts (1.0 mol) of glycerin monomethacrylate monooctanoate obtained in Preliminary Synthesis Example 2 and 249 parts of methyl methacrylate. And 0.5 parts of di-n-butyltin dilaurate were placed in a reaction vessel, kept at 50 ° C. and stirred,
Furthermore, 87 parts of 2,4-tolylene diisocyanate (0.5
Mol) was added dropwise over 30 minutes. At this time, the reaction heat was generated, but the reaction temperature was kept at 50 to 60 ° C. After that, 60 ℃
The temperature was maintained for 1 hour to prepare an unsaturated urethane resin a-3 containing 60% of unsaturated urethane A-3 and 40% of methyl methacrylate.

Preparation of Unsaturated Urethane Resin r-1 In the preparation of unsaturated urethane resin a-1, unsaturated urethane resin a- was used except that the amount of polyoxypropylene glycol (molecular weight 200) diacrylate used was 41 parts.
90% of unsaturated urethane A-1 in the same manner as in the preparation of 1.
And polyoxypropylene glycol (molecular weight 200)
Unsaturated urethane resin r-1 containing 10% diacrylate
Was prepared.

Preparation of unsaturated urethane resin r-2: 6 parts of unsaturated urethane resin a-1 and 94 parts of polyoxypropylene glycol (molecular weight 200) diacrylate are mixed and dissolved to prepare unsaturated urethane A-1 of 3 parts. % And 97% of polyoxypropylene glycol (molecular weight 200) diacrylate, an unsaturated urethane resin r-2 was prepared.

Preparation of Unsaturated Urethane Resin r-3 In the preparation of unsaturated urethane resin a-3, except that the amount of methyl methacrylate used was 41 parts, the procedure of the unsaturated urethane resin a-3 was as follows. Unsaturated urethane A-
An unsaturated urethane resin r-3 containing 90% of 3 and 10% of methyl methacrylate was prepared.

Preparation of unsaturated urethane resin r-4: 5 parts of unsaturated urethane resin a-3 are mixed and dissolved with 95 parts of methyl methacrylate to give 3% of unsaturated urethane A-3.
And an unsaturated urethane resin r-4 containing 97% of methyl methacrylate was prepared.

Synthesis of unsaturated urethane B-1 and preparation of unsaturated urethane resin b-1 111 parts (0.5 mol) of isophorone diisocyanate,
100 parts of dry toluene and 0.5 part of di-n-butyltin dilaurate were placed in a reaction vessel, kept at 50 ° C. and stirred, and further diethylene glycol monomethacrylate 87 was added.
Part (0.5 mol) was added dropwise over 30 minutes. During this period, the reaction temperature was kept at 50 to 60 ° C. After that, 50-55 ℃
And the reaction was terminated when the remaining amount of isocyanate groups in the reaction product became 1/2 of the theoretical amount calculated from the amount of diisocyanate used in the reaction. The reaction product obtained here is unsaturated urethane monoisocyanate in which isophorone diisocyanate and diethylene glycol monomethacrylate are bonded at a 1/1 (molar ratio). Next, this reaction product was maintained at 60 ° C. and stirred, and further 136 parts (0.5 mol) of glycerin monoacrylate / monooctanoate obtained in Preliminary Synthesis Example 1 was added dropwise over 30 minutes. At this time, reaction heat is generated, but the reaction temperature is 60 to 70 ° C.
Kept at. Then, it hold | maintained at 70 degreeC for 2 hours, and unsaturated urethane B-1 was synthesize | combined. Further, 334 parts of neopentyl glycol diacrylate was added and dissolved, and toluene was distilled off under reduced pressure to obtain an unsaturated urethane resin b-1 containing 50% of unsaturated urethane B-1 and 50% of neopentyl glycol diacrylate. Was prepared.

Synthesis of unsaturated urethane B-2, R-5 and preparation of unsaturated urethane resin b-2, r-5 Synthesis of unsaturated urethane B-1 and unsaturated urethane resin b
In the same manner as in the preparation of -1, unsaturated urethane B-2 was synthesized, unsaturated urethane resin b-2 was synthesized, unsaturated urethane R-5 was synthesized, and unsaturated urethane resin r-5 was prepared.

Synthesis of unsaturated urethane B-3 and preparation of unsaturated urethane resin b-3 87 parts (0.5 mol) of 2,4-tolylene diisocyanate, 249 parts (2.49 mol) of methyl methacrylate.
And 0.5 part of di-n-butyltin dilaurate were placed in a reaction vessel, kept at 50 ° C. and stirred, and 199 parts (0.5 mol) of glycerin monomethacrylate monoisopalmitate obtained in Preliminary Synthesis Example 3 was further added. It dripped over 30 minutes. During this period, the reaction temperature was kept at 50 to 60 ° C. Then 50
The reaction was continued at ˜55 ° C., and the reaction was terminated when the residual amount of isocyanate groups in the reaction product became 1/2 of the theoretical amount calculated from the amount of diisocyanate used in the reaction. The reaction product obtained here is an unsaturated urethane monoisocyanate in which 2,4-tolylene diisocyanate and glycerin monomethacrylate monoisopalmitate are bonded at a 1/1 (molar ratio). Next, this reaction product was maintained at 60 ° C. and stirred, and 87 parts (0.5 mol) of diethylene glycol monomethacrylate was further added dropwise over 30 minutes. At this time, the reaction temperature was maintained at 60 to 70 ° C. Then 70
The temperature was kept at 2 ° C for 2 hours to prepare an unsaturated urethane resin b-3 containing 60% of unsaturated urethane B-3 and 40% of methyl methacrylate.

Synthesis of unsaturated urethane R-6 and preparation of unsaturated urethane resin r-6 Synthesis of unsaturated urethane A-3 and unsaturated urethane resin a
In the same manner as in Preparation of -3, unsaturated urethane R-6 was synthesized and unsaturated urethane resin r-6 was prepared.

[0056]

[Table 1]

[0057]

[Table 2]

In Tables 1 and 2, the numerical value of the used amount: the numerical value in parentheses of the used amount: mol * 1: polyoxypropylene glycol (molecular weight 20
0) Diacrylate * 2: Neopentyl glycol diacrylate * 3: Methyl methacrylate ** 1: Glycerin monoacrylate monooctanoate ** 2: Glycerin monomethacrylate monooctanoate ** 3: Glycerin monomethacrylate mono Isopalmitate ** 4: Diethylene glycol monomethacrylate ** 5: Glycerine dimethacrylate ** 6: Hydroxyethyl acrylate ** 7: 2,4-Tolylene diisocyanate ** 8: Polymethylene polyphenyl isocyanate (N
CO group average 3) ** 9: Isophorone diisocyanate

Test Category 3 (Production of Crosslinked Polymer Particles) Crosslinked polymer particles Pa-1 to Pa-3, Pb-1 to Pb-
3, Pr-1 to Pr-6 were produced as follows. The contents are summarized in Table 3.

Example 1 (Production of Crosslinked Polymer Particles Pa-1 by Suspension Polymerization) The unsaturated urethane resin a-1 prepared in Test Section 2 was used.
Parts, 3 parts calcium phosphate, 2 parts 1% aqueous solution of sodium dodecylbenzenesulfonate and 0.2 parts dibenzoyl peroxide, 80 parts of ion-exchanged water are added, and the mixture is dispersed with a homomixer and further homogenized. Dispersed evenly. The temperature was raised to 70 ° C. with stirring, and the temperature was kept at 70 to 80 ° C. for 24 hours to complete the radical polymerization. A 0.1 N hydrochloric acid aqueous solution was added to the reaction system to adjust the pH of the reaction system to 3. The produced particles are filtered off, and washing with water and filtration are repeated until the washing water becomes neutral.
After drying, crosslinked polymer particles Pa-1 were obtained. The crosslinked polymer particles Pa-1 obtained here were spherical particles having an average particle diameter of 15 μm.

Examples 2 and 3 and Comparative Examples 1 to 4 (crosslinked polymer particles Pa-2, Pa-3 and Pr produced by the suspension polymerization method)
Production of -1 to Pr-4) Production was carried out in the same manner as for the crosslinked polymer particles Pa-1. With respect to the obtained crosslinked polymer particles, the shape was observed and the average particle size was measured, and the results are shown in Table 3.

Example 4 (Production of Crosslinked Polymer Particles Pb-1 by Emulsion Polymerization Method) 30 unsaturated urethane resin b-1 prepared in Test Category 2 was used.
Parts, partially saponified polyvinyl alcohol (molecular weight about 20,000)
6 parts, 1% of sodium dodecylbenzene sulfonate
After 6 parts of the aqueous solution and 0.3 part of ammonium persulfate, the above components were added to 70 parts of ion-exchanged water and dispersed by a homomixer, the mixture was further uniformly dispersed by a homogenizer. The temperature was raised to 70 ° C. with stirring, and the temperature was kept at 70 to 80 ° C. for 24 hours to complete the radical polymerization. 100 parts of saturated sodium sulfate aqueous solution was added to the reaction system, stirred, and then allowed to stand. The produced particles were separated by filtration, repeatedly washed with water several times, and dried to obtain crosslinked polymer particles Pb-1. The crosslinked polymer particles Pb-1 obtained here were spherical particles having an average particle diameter of 0.7 μm.

Examples 5 and 6 and Comparative Examples 5 and 6 (crosslinked polymer particles Pb-2, Pb-3 and Pr by emulsion polymerization method)
Production of -5 and Pr-6) Production was carried out in the same manner as for the crosslinked polymer particles Pb-1. With respect to the obtained crosslinked polymer particles, the shape was observed and the average particle size was measured, and the results are shown in Table 3.

Regarding the crosslinked polymer particles obtained above,
The solubility in the unsaturated urethane resin used as a raw material was determined by the following method. The results are shown in Table 3. .. Solubility evaluation method: 0.5 part of the crosslinked polymer particles and 10 parts of the unsaturated urethane resin used in the synthesis of the crosslinked polymer particles are placed in a beaker and kept at 40 ° C. and a magnetic stirrer is used for 30 times. After stirring for minutes, the dissolved state was observed.

[0065]

[Table 3]

Test Category 4 (Preparation of Composition and Curing Molding by Optical Stereolithography Method and Evaluation of Cured Molded Product) Examples 7 to 14 and Comparative Examples 7 to 22 (Preparation of Composition) 4 or 100 parts by weight of the unsaturated urethane resin shown in Table 5, 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator (trade name Irgacure 18
4, manufactured by Ciba-Geigy) and 5 parts by weight of the crosslinked polymer particles shown in Table 4 or Table 5 in a mixing container at a ratio shown in Table 4 or Table 5 and stirred until uniform using a paint shaker. By mixing, an unsaturated urethane resin composition was prepared. In Comparative Examples 13 to 16, thermoplastic polymers were used which were previously uniformly dissolved in 100 parts by weight of the unsaturated urethane resin at the ratio shown in Table 5.

Production of cured product and its evaluation Three-dimensional N equipped with a container filled with the composition prepared above.
By using an optical three-dimensional modeling apparatus mainly composed of a C table and a helium / cadmium laser light (wavelength 3250 angstrom) control system, the surface of the composition is irradiated with helium / cadmium laser light focused from the vertical direction, A disk having a diameter of 150 mm and a thickness of 10 mm was formed. Then, the shaped disk was cut into a length 127 mm × width 12.7 mm using a diamond cutter to prepare a test piece. With respect to this test piece, the light transmittance was measured as an evaluation of curing shrinkage and transparency by the following method. The results are shown in Tables 4 and 5.

Curing shrinkage: The density D _{1 of the} test piece and the density D ₂ of the radical curable resin used for modeling were measured, and the curing shrinkage was calculated by the following formula. Curing shrinkage rate (%) = [{(1 / D ₂ ) − (1 / D ₁ )} /
(1 / D ₂ )] × 100 ・ ・ Light transmittance: 700 nm in the thickness direction (10 mm) of the test piece
The light transmittance (T%) was measured by a spectrophotometer.

[0069]

[Table 4]

[0070]

[Table 5]

In Tables 4 and 5, a-1, a-2, b-1, b-2: unsaturated urethane resins Pa-1, Pa-2, Pb-1, prepared in Test Category 2
Pb-2, Pr-1, Pr-2, Pr-5: Test category 3
Crosslinked polymer particles produced in step * 4: Silica fine particles (average particle size 1.2 μm) * 5: Styrene-divinylbenzene crosslinked copolymer particles (average particle size 20 μm) * 6: Polymethylmethacrylate (average molecular weight 5000
0) * 7: Polypropylene diadipate (average molecular weight 550
0)

Test Category 5 (Preparation of Composition and Curing Molding by Radical Polymerization Using the Same and Evaluation of Cured Molded Product) Examples 15 to 20 and Comparative Examples 23 to 32 (Preparation of Composition) As materials to be used Unsaturated urethane resin 100 shown below
In the same manner as in Test Category 4, except that 1 part by weight of methyl ethyl ketone peroxide was used as a radical polymerization initiator and 0.0075 parts by weight of cobalt naphthenate was used as a curing accelerator, the composition of the proportions shown in Table 6 was used. The thing was prepared.

Production of cured product and its evaluation The composition prepared above was applied to a glass plate (25 cm) having a thickness of 5 mm.
Two (25 x 25 cm) polyethylene tubes each having an outer diameter of 5 mm were sandwiched and poured into a casting tank having a clearance of 3 mm, and the casting tank was held in a constant temperature bath at 35 ° C for 2 hours to obtain a cured molded product. Remove this cured molded product from the casting tank and
Post cure was carried out at 0 ° C. for 12 hours. The cured molded product obtained here was subjected to the following test. The results are shown in Table 6.

· Appearance of cured product: The degree of warpage and cracks was visually observed and judged according to the following criteria. ⊚: No cracks or warpages at all ○: Almost no cracks or warpages △: Slight cracks or warpages ×: Many cracks or warpages ・ Light transmittance: Performed in the same manner as in Test Category 4 It was

[0075]

[Table 6]

[0076]

As is apparent from the above, the present invention described above has an effect of preventing shrinkage of an unsaturated urethane resin during curing and molding, and at the same time improving transparency of a cured and molded product obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-306214 (JP, A) JP-A-5-178946 (JP, A) JP-A-4-293909 (JP, A) JP-A-3- 37202 (JP, A) JP-A-6-322039 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 299/00-299/08 C08F 290/00-290/14 C08G 18/67

Claims (13)

(57) [Claims] 1. A modifier for an unsaturated urethane resin for curing and molding, which comprises crosslinked polymer particles obtained by radically polymerizing the following unsaturated urethane resin. Unsaturated urethane resin: One or more kinds of unsaturated urethane selected from the unsaturated urethane represented by the following formula 1 and the unsaturated urethane represented by the following formula 2, and copolymerizable with the unsaturated urethane An unsaturated urethane resin in which (meth) acrylic acid ester is in a ratio of the unsaturated urethane / the (meth) acrylic acid ester = 80/20 to 20/80 (weight ratio). [Formula 1] [Formula 2] [In Formulas 1 and 2, X ¹ , X ² are residues Y ¹ , Y ² , Y ^{3 obtained} by removing an isocyanate group from a polyisocyanate selected from diisocyanates and triisocyanates: a residue obtained by removing a hydroxyl group from a trivalent alcohol. group Y ^4: polyhydric alcohols, residues R ^1, excluding the hydroxyl group from the divalent or trivalent polyols selected from polyether polyols and polyester ^{polyols, R 3, R 5, R} 7, R 8: H or CH ₃ R ² , R ⁴ , R ⁶ : an aliphatic hydrocarbon group having 5 to 21 carbon atoms, j, k, m, n: 1 or 2, and satisfying j + k = 2 or 3, and m + n = 2 or 3 Satisfying p, q: 0 to 2 and satisfying p + q = 1 or 2] 2. A cure according to claim 1 wherein at least one of R ¹ and R ³ of formula 1 is H and at least one of R ⁵ , R ⁷ and R ⁸ of formula 2 is H. Unsaturated urethane resin modifier for molding. 3. An unsaturated urethane resin is constituted (meth).
Acrylic ester is an acrylic ester of one or two or more polyols selected from alcohols, polyether polyols, polyester polyols and alkoxylated bisphenols, each of which has a valence of 2 to 4, or the polyol and acrylic acid and methacrylic acid. The modifier of the unsaturated urethane resin for curing and molding according to claim 1 or 2, which is a (meth) acrylate mixed with. 4. The modifier for an unsaturated urethane resin for curing and molding according to claim 1, 2 or 3, wherein the crosslinked polymer particles have an average particle diameter of 0.1 to 100 μm. 5. The modifier for a curable unsaturated urethane resin according to claim 1, 2, 3 or 4, wherein the crosslinked polymer particles are radically polymerized by a suspension polymerization method or an emulsion polymerization method. 6. The modifying agent according to claim 1, 2, 3, 4 or 5 is added to 50 parts by weight of the unsaturated urethane resin.
An unsaturated urethane resin composition for curing and molding, which is contained in a proportion of 300 parts by weight. 7. The unsaturated urethane resin composition for curing and molding according to claim 6, wherein the unsaturated urethane resin is the following unsaturated urethane resin. Unsaturated urethane resin: One or more kinds of unsaturated urethane selected from the unsaturated urethane represented by the following formula 3 and the unsaturated urethane represented by the following formula 4, and copolymerizable with the unsaturated urethane An unsaturated urethane resin in which (meth) acrylic acid ester is in a ratio of the unsaturated urethane / the (meth) acrylic acid ester = 80/20 to 20/80 (weight ratio). [Formula 3] [Formula 4] [In Formula 3 and Formula 4, X ³ , X ⁴ : Residues obtained by removing isocyanate group from polyisocyanate selected from diisocyanate and triisocyanate Y ⁵ , Y ⁶ , Y ⁷ : trivalent alcohol group Y ^8: polyhydric alcohols, residues removing hydroxyl groups from a divalent or trivalent polyols selected from polyether polyols and polyester polyols ^{R 9, R 11, R 13} , R 15, R 16: H or CH ₃ R ¹⁰ , R ¹² , R ¹⁴ : an aliphatic hydrocarbon group having 5 to 21 carbon atoms r, s, t, u: 1 or 2, and satisfying r + s = 2 or 3, and t + u = 2 or 3 Satisfying v, w: 0 to 2 and satisfying v + w = 1 or 2] 8. The cure according to claim 7, wherein at least one of R ⁹ and R ¹¹ of formula 3 is H, and at least one of R ¹³ , R ¹⁵ and R ¹⁶ of formula 4 is H. Unsaturated urethane resin composition for molding. 9. An unsaturated urethane resin is constituted (meth).
Acrylic ester is an acrylic ester of one or two or more polyols selected from alcohols, polyether polyols, polyester polyols and alkoxylated bisphenols, each of which has a valence of 2 to 4, or the polyol and acrylic acid and methacrylic acid. The unsaturated urethane resin composition for curing and molding according to claim 7 or 8, which is a mixed (meth) acrylate with. 10. The unsaturated urethane constituting the unsaturated urethane resin is the unsaturated urethane represented by the formula 3, and the unsaturated urethane constituting the unsaturated urethane resin which forms the modifier is represented by the formula: The unsaturated urethane resin composition for curing and molding according to claim 8 or 9, which is the unsaturated urethane represented by 1. 11. The unsaturated urethane constituting the unsaturated urethane resin is the unsaturated urethane represented by the formula 4, and the unsaturated urethane constituting the unsaturated urethane resin which forms the modifier is represented by the formula: The unsaturated urethane resin composition for curing and molding according to claim 8 or 9, which is the unsaturated urethane represented by 2. 12. The method according to claim 6, 7, 8, 9, 10 or 11.
A method for curing molding, which comprises curing and molding the unsaturated urethane resin composition for curing and molding described above. 13. A method for curing and molding, comprising curing and molding the unsaturated urethane resin composition for curing and molding according to claim 8, 9, 10 or 11 by photopolymerization.