JP3377601B2 - 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 fine inorganic particles (Japanese Patent Laid-Open No. 1-232025), 3) means for containing fine particles of a crosslinked polymer insoluble in a radical curable resin, for example, styrene-containing unsaturated polyester resin. Examples containing fine particles of divinylbenzene copolymer cross-linked polymer (JP-A-48-81984), 4) Resin fine particles having a density close to that of a radical curable resin and having no reactivity with the radical curable resin. Means for containing powder (Japanese Patent Laid-Open No. 5-286)
040) and so on.

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) and 4) 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 provides crosslinked polymer particles obtained by radically polymerizing the following unsaturated urethane resin, wherein the radical polymerization is 5 to 60 mol% of all radically polymerizable groups contained in the unsaturated urethane resin. The present invention relates to a modifier comprising a crosslinked polymer particle containing a functional group as an unreacted radically polymerizable group, a composition containing the modifier, and a method for curing and molding the composition. Unsaturated urethane resin: One or more unsaturated monools selected from the unsaturated monools represented by the following formula 1 and the unsaturated monools represented by the following formula 2 and the diisocyanate compound are unsaturated. The unsaturated urethane obtained by the urethanization reaction at a ratio of monool / the diisocyanate compound = 2/1 (molar ratio) and the (meth) acrylic acid ester copolymerizable with the unsaturated urethane are the unsaturated compounds. Urethane / (meth) acrylic acid ester = 80
An unsaturated urethane resin having a ratio of / 20 to 20/80 (weight ratio).

[0007]

[Formula 1]

[0008]

[Formula 2]

In the formulas 1 and 2, Y ¹ is a residue Y ² : trivalent in which a hydroxyl group is removed from a divalent or trivalent polyol selected from polyhydric alcohols, polyether polyols, polyester polyols and polyether ester polyols. Residues obtained by removing a hydroxyl group from alcohol R ¹ , R ² : H or CH ₃ R ³ : an aliphatic hydrocarbon group having 5 to 21 carbon atoms m: 1 or 2

The modifier of the present invention comprises specific crosslinked polymer particles obtained by radical polymerization of an unsaturated urethane resin. In addition, the above-mentioned unsaturated urethane resin is such that a specific unsaturated urethane and a (meth) acrylic acid ester copolymerizable with the specific unsaturated urethane are each contained in a predetermined ratio. The unsaturated urethane constituting the unsaturated urethane resin is 1) an unsaturated monool represented by the formula 1 / diisocyanate compound = urethane reaction product of 2/1 (molar ratio), 2) an unsaturated represented by the formula 2. Urethane reaction product of monool / diisocyanate compound = 2/1 (molar ratio), 3) Unsaturated monool represented by Formula 1 / unsaturated monool represented by Formula 2 / diisocyanate compound = 1/1/1 ( (Molar ratio) of the urethanization reaction product.

The unsaturated monol represented by the formula 1 is 1)
A partial ester obtained from 1 mol of (meth) acrylic acid and 1 mol of a diol, and 2) a partial ester obtained from 2 mol of (meth) acrylic acid and 1 mol of triol,
Both have one free hydroxyl group in the molecule.

The diol and triol used for synthesizing the monool represented by the formula 1 are 1) di- or trihydric alcohol, 2) polyether diol, polyether triol, 3) polyester diol, polyester triol, 4 ) Polyether ester diol and polyether ester triol are mentioned.

As the monool represented by the formula 1, 1)
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 1,6
-Mono (meth) acrylate of divalent alcohol such as hexanediol monoacrylate, 2) glycerin diacrylate, glycerin dimethacrylate, trimethylolpropane dimethacrylate, 5-methyl-1,
2,4-heptanetriol dimethacrylate, 1,
3, such as 2,6-hexanetriol dimethacrylate
Mono (meth) acrylates of polyether diols such as di (meth) acrylates of polyhydric alcohols, 3) polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, 4) ethylene glycol monoglyceryl ether dimethacrylate, (poly)
(Poly) ethertriol di (meth) acrylates such as ethoxylated trimethylolpropane dimethacrylate, (poly) propoxylated trimethylolpropane dimethacrylate, 5) Polycaprolactone diol monomethacrylate, polyneopentyl adipate diol monoacrylate, etc. Diesters of polyester triol such as poly (caprolactone triol diacrylate) starting from mono (meth) acrylate of polyester diol, 6) trivalent alcohol as starting material, and polycaprolactone triol dimethacrylate starting from trihydric alcohol. (Meth) acrylate is mentioned.

As the diol or triol used for synthesizing the unsaturated monool represented by the formula 1, those having a molecular weight of 200 or less per hydroxyl group contained in the molecule can be advantageously used, but 150 or less. Can be used particularly advantageously.

The unsaturated monool represented by the formula 2 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. It is a partial ester.

The trihydric alcohol used for synthesizing the unsaturated monool represented by the formula 2 is glycerin,
Trimethylolethane, trimethylolpropane, 1,
2,6-hexanetriol and the like can be mentioned.

The long-chain fatty acid used for synthesizing the unsaturated monool represented by the formula 2 is a saturated or unsaturated fatty acid having 6 to 22 carbon atoms and having a linear or branched chain. Examples of such long-chain fatty acids include 1) linear saturated fatty acids such as hexanoic acid, octanoic acid, dodecanoic acid and stearic acid, 2) branched saturated fatty acids such as isooctanoic acid, isopalmitic acid and isostearic acid, and 3) olein. Acids, unsaturated fatty acids such as elaidic acid, and mixtures thereof.

As the unsaturated monool represented by the formula 2, 1) glycerin monomethacrylate monooctanoate, trimethylolpropane monoacrylate monoisononanoate, 5-methyl-1,2,4-heptanetriol mono Methacrylate monooleate,
1,2,6-hexanetriol monomethacrylate
Examples thereof include mono-2-ethylhexoate, and glycerin mono (meth) acrylic acid / mono long-chain fatty acid mixed ester monool can be advantageously used.

As the diisocyanate compound to be reacted with the unsaturated monool represented by the formula 1 or the unsaturated monool represented by the formula 2 as exemplified above, 1) various tolylene diisocyanates and methylene-bis- (4-) Aromatic diisocyanates such as phenyl isocyanate), 2)
Hexamethylene diisocyanate, methylene-bis-
Aliphatic diisocyanate or alicyclic diisocyanate such as (4-cyclohexyl isocyanate), 3) 4-isocyanatomethyl-1-isocyanato-1-methyl-cyclohexane, 5-isocyanatomethyl-1-isocyanato-1,1-dimethyl Aliphatic / alicyclic diisocyanates such as -5-methyl-cyclohexane (isophorone diisocyanate), 4) Polyether diols such as polyethylene glycol and polypropylene glycol, and diols represented by polyester diols such as polycaprolactone diol and neopentyl adipate A urethane diisocyanate obtained from 1 mol and 2 mol of the above-mentioned diisocyanate can be used.

In the unsaturated urethane obtained by using the unsaturated monool represented by the formula 1, the same unsaturated monool can be used, or different unsaturated monools can be used. In the unsaturated urethane obtained by using the unsaturated monool represented by the formula 2, the same unsaturated monool can be used, or different unsaturated monools can be used.

When different unsaturated monools are used, the unsaturated urethane obtained is an asymmetric unsaturated urethane. The diisocyanate compound used for synthesizing such an asymmetrical unsaturated urethane has an isocyanate group which is influenced by a sterically hindering substituent and an isocyanate group which is not influenced by the same, or an aliphatic carbonized compound. Those having an isocyanate group bonded to a hydrogen group and an isocyanate group bonded to an aromatic hydrocarbon group, and the like, it is preferable to use a diisocyanate compound having mutually different isocyanate groups, as the diisocyanate compound, 2, 4-
Tolylene diisocyanate, isophorone diisocyanate, 4-isocyanatomethyl-1-isocyanato-1-
Methyl-cyclohexane etc. are mentioned.

The present invention is not particularly limited to the method for synthesizing unsaturated urethane, and a known method, for example, the method described in Japanese Patent Application Laid-Open No. 4-53809 can be applied to the synthesis, but it is asymmetric. In order to synthesize a form-unsaturated urethane, 1 mol of an unsaturated monool is reacted with 1 mol of a diisocyanate compound having an isocyanate group having different reactivity as described above to obtain an unsaturated urethane monoisocyanate, and then an unsaturated monounsaturation different from this is used. The method of reacting monool is preferred.

As the (meth) acrylic acid ester constituting the unsaturated urethane resin, 1) butyl acrylate,
Alkyl acrylates such as 2-ethylhexyl acrylate, 2) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and isobutyl methacrylate, 3) Dihydric alcohols such as ethylene glycol diacrylate, neopentyl glycol diacrylate and dicyclopentene dimethylene diacrylate. Acrylate, 4) 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, etc.,
Dihydric alcohol dimethacrylate, 5) Trihydric alcohol triacrylate such as glycerin triacrylate and trimethylolpropane triacrylate, 6) Trihydric alcohol trimethacrylate such as glycerin trimethacrylate and trimethylolethane trimethacrylate, 7 ) Trimethylolpropane diacrylate
Mixed (meth) acrylates of trihydric alcohols such as monomethacrylate and glycerin monoacrylate / dimethacrylate, 8) tetrahydric alcohol tetra (s) such as pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate / dimethacrylate, etc. (Meth) acrylate,
9) Polyether polyol poly (obtained from a polyether polyol obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide to the above-mentioned dihydric or tetrahydric alcohol, acrylic acid, methacrylic acid or a mixed acid thereof. (Meth) acrylate, 10) Polyester polyol poly (meth) obtained from a polyester polyol obtained by adding an aliphatic lactone such as caprolactone or butyrolactone to the above-mentioned dihydric or tetrahydric alcohol, acrylic acid, methacrylic acid, or a mixed acid thereof. Acrylate, 11) Di (meth) acrylate of alkoxylated bisphenol 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 is more than the above range, the crosslinked polymer particles obtained from such an unsaturated urethane resin will be insufficient in exhibiting the desired effect as a modifier.

The crosslinked polymer particles used as the modifier of the present invention are obtained by radical polymerization of the unsaturated urethane resin as described above, and all radical-polymerizable groups contained in the unsaturated urethane resin. Among them, 5 to 60 mol%, preferably 10 to 40% of radical-polymerizable groups are contained as unreacted radical-polymerizable groups.

The unsaturated urethane and (meth) acrylic acid ester to be used for preparing the above-mentioned crosslinked polymer particles can be arbitrarily selected from the above-mentioned ones and can be used. In order to better develop the desired effect as a modifier, particularly in order to better develop the desired effect in the curing and molding by photopolymerization described later, as unsaturated urethane, acryloxy in the molecule. A urethane-reacted one using an unsaturated monool having a group is preferable. Specific examples of the unsaturated monool include an unsaturated monool in which R ¹ is H in the case of m = 1 in the formula 1, and one or both of R ¹ in the case of m = 2 in the formula 1 are H. And unsaturated monools of formula 2 in which R ² is H. The (meth) acrylic acid ester used in combination with these unsaturated urethanes is one or two selected from alcohols, polyether polyols, polyester polyols, polyether ester polyols and alkoxylated bisphenols, each of which has 2 to 4 valences. Preference is given to using acrylic esters of one or more polyols.

As a method of radically polymerizing an unsaturated urethane resin to obtain crosslinked polymer particles, 1) a radical polymerization of an unsaturated urethane resin is carried out by a known solution polymerization method or a bulk polymerization method, and then the obtained crosslinked polymer 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.

In the preparation of the crosslinked polymer particles, there are various methods for controlling the content ratio of the unreacted radically polymerizable group, which includes, for example, 1) all of the unsaturated urethane resins contained in the unsaturated urethane resin used. Method of radical polymerization at a temperature condition at least 10 ° C. lower than the glass transition temperature of the polymer obtained by participating in radical polymerization reaction in which 95 mol% or more of the radical polymerizable groups are involved, 2) a polymerization inhibitor Method of adding at any time during radical polymerization, 3) adding a solvent that becomes a poor solvent to the polymer produced in solution polymerization at any time during radical polymerization, and producing a polymer from the reaction system Examples include a method of separating by precipitation.

The ratio of the unreacted radically polymerizable groups remaining in the crosslinked polymer particles to the total radically polymerizable groups contained in the unsaturated urethane resin is determined by the unsaturated urethane resin used in the preparation of the crosslinked polymer particles and Fourier exchange infrared spectroscopy (FT-IR) for both crosslinked polymer particles
From the IR spectrum using, the wavenumbers corresponding to the ester carbonyl group and the olefinic double bond (for example, 1
The area ratio at 740 cm ^-1 and 1640 cm ^-1 ) was measured,
It can be calculated from the value of these area ratios. FT-
For the IR method, the transmission FT-IR method based on the KBr method is simple and convenient.

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 are a crosslinked structure, they do not dissolve or swell with the unsaturated urethane resin in the composition of the present invention as described below, and the composition It prevents shrinkage during curing 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 30 to 300 parts by weight, preferably 40 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 30 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 resin used in the composition of the present invention, but the following unsaturated urethane resins are preferably used. Unsaturated urethane resin: One or more unsaturated monools selected from unsaturated monools represented by the following formula 3 and unsaturated monools represented by the following formula 4 and the diisocyanate compound are unsaturated. The unsaturated urethane obtained by the urethanization reaction at a ratio of monool / the diisocyanate compound = 2/1 (molar ratio) and the (meth) acrylic acid ester copolymerizable with the unsaturated urethane are the unsaturated compounds. Urethane / the (meth) acrylic acid ester = 80 / 20-
An unsaturated urethane resin composed of a ratio of 20/80 (weight ratio).

[0033]

[Formula 3]

[0034]

[Formula 4]

In the formulas 3 and 4, Y ³ is a residue Y ⁴ : trivalent in which a hydroxyl group is removed from a divalent or trivalent polyol selected from polyhydric alcohols, polyether polyols, polyester polyols and polyether ester polyols. residues removing hydroxyl groups from an alcohol R ^4, R ^5: H or CH ₃ R ^6: aliphatic hydrocarbon group of 5 to 21 carbon atoms n: 1 or 2

In the composition of the present invention, the formula 3 representing an unsaturated monool used in the production of unsaturated urethane constituting the unsaturated urethane resin is represented by the formula 3 which is the unsaturated urethane resin used in the preparation of the crosslinked polymer particles. Corresponding to the formula 1 showing the unsaturated monool used in the production of the unsaturated urethane constituting the formula (1), the formula 4 also corresponds to the formula 2, and the formula 1 and the formula 2 are as described above. Here, the description of Equations 3 and 4 is omitted. Further, the (meth) acrylic acid ester constituting the unsaturated urethane resin is the same as the (meth) acrylic acid ester constituting the unsaturated urethane resin used for the preparation of the crosslinked polymer particles as the modifier,
Since this is also 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 used for the preparation of the crosslinked polymer particles as the modifier has been described above. It can be arbitrarily selected from the above, but 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, it is preferable that the unsaturated urethane is subjected to a urethanization reaction using an unsaturated monool having an acryloxy group in the molecule. Specific examples of the unsaturated monool include an unsaturated monool in which R ⁴ is H when n = 1 in Formula 3,
In the case of n = 2, an unsaturated monool in which one or both of R ⁴ is H and an unsaturated monool in the case where R ⁵ is H in formula 4 are included. Further, as the (meth) acrylic acid ester used in combination with these unsaturated urethane,
It is preferable to use an acrylic acid ester of one or more polyols selected from alcohols, polyether polyols, polyester polyols, polyether ester polyols and alkoxylated bisphenols, each having a valency of 2 to 4.

In the same sense, when the unsaturated monool used for producing the unsaturated urethane constituting the unsaturated urethane resin of the composition of the present invention is the unsaturated monool represented by the formula 3, modification is carried out. The unsaturated monool used in the production of the unsaturated urethane constituting the unsaturated urethane resin that forms the agent is preferably the unsaturated monool represented by the formula 1. Further, when the unsaturated monool used for producing the unsaturated urethane constituting the unsaturated urethane resin of the composition of the present invention is the unsaturated monool represented by the formula 4, a modifier is formed. The unsaturated monool used in the production of the unsaturated urethane constituting the unsaturated urethane resin is preferably the unsaturated monool represented by the formula 2. Further, as the unsaturated monool used for producing the unsaturated urethane constituting the unsaturated urethane resin of the composition of the present invention, both the unsaturated monool represented by the formula 3 and the unsaturated monool represented by the formula 4 are used. In this case, the unsaturated monool used in the production of the unsaturated urethane constituting the unsaturated urethane resin that forms the crosslinked polymer particles is the unsaturated monool represented by the formula 1 and the unsaturated monool represented by the formula 2. It is preferable to use both monools.

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, and energy rays such as ultraviolet rays and electron beams can be used in the presence of a photopolymerization initiator. It can be cured and molded by photopolymerization. In the composition of the present invention, the unsaturated urethane resin and the modifier participate in the polymerization reaction with each other at the time of curing and molding, and thus the obtained cured and molded product becomes an integrally molded product, so that the cured and molded product is prevented from shrinking. And transparency can be imparted at the same time. In the case of a cured molded article obtained by a conventionally known method in which inorganic particles, particles of a thermoplastic polymer, particles of a cured resin that is almost completely cured, or the like are contained as a modifier, the above-mentioned modifier is used. And the unsaturated urethane resin do not react with each other, and thus the modifier and the unsaturated urethane resin cured product are individually present in the obtained cured molded product, so that the difference in their refractive index and the thermal expansion coefficient Due to the difference or due to the generation of fine bubbles and fine cracks during curing and molding, only a cured and cured product having low transparency can be obtained.

The composition of the present invention is particularly effective for 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, As a result, 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 as a polymerizable group in the molecule. Among them, as described above, the formula 1
When the unsaturated urethane obtained from the unsaturated monol represented by the formula (3) is used, it is preferable to use the unsaturated urethane obtained from the unsaturated monol represented by the formula 3 in the composition using the modifier. Further, when an unsaturated urethane obtained from the unsaturated monol represented by the formula 2 is used as the modifier, a composition using the modifier is an unsaturated urethane obtained from the unsaturated monool represented by the formula 4. Is preferably used. Further, when an unsaturated urethane obtained from both the unsaturated monool represented by the formula 1 and the unsaturated monool represented by the formula 2 is used as the modifier, the composition using the modifier is represented by the formula 3 It is preferable to use an unsaturated urethane obtained from both the unsaturated monool represented by (4) and the unsaturated monool represented by formula (4). The (meth) acrylic acid ester used in combination with these unsaturated urethanes is one or two selected from alcohols, polyether polyols, polyester polyols, polyether ester polyols and alkoxylated bisphenols, each of which has 2 to 4 valences. Preference is given to using acrylic esters of one or more polyols.

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.

[0043]

【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 The same procedure as in Preliminary Synthesis Example 1 was carried out 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, A-3 and preparation of unsaturated urethane resin a-2, a-3 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 is synthesized and unsaturated urethane resin a-2 is prepared, and unsaturated urethane A-3 is synthesized and unsaturated urethane resin a-
Preparation of 3 was performed. However, in these syntheses and preparations, the unsaturated monool and the diisocyanate compound were reacted in one step without passing through the unsaturated urethane monoisocyanate.

Synthesis of unsaturated urethane A-4 and preparation of unsaturated urethane resin a-4 286 parts (1.0 mol) of glycerin monomethacrylate monooctanoate and 249 parts of methyl methacrylate obtained in Preliminary Synthesis Example 2. 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-4 containing 60% of unsaturated urethane A-4 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 give 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-4, the procedure of preparation of unsaturated urethane resin a-4 was repeated except that the amount of methyl methacrylate used was 41 parts. Unsaturated urethane A-
An unsaturated urethane resin r-3 containing 90% of 4 and 10% of methyl methacrylate was prepared.

Preparation of unsaturated urethane resin r-4: 5 parts of unsaturated urethane resin a-4 and 95 parts of methyl methacrylate are mixed and dissolved to give 3% of unsaturated urethane A-4.
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, B-3 and preparation of unsaturated urethane resin b-2, b-3 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 is synthesized and unsaturated urethane resin b-2 is prepared, and unsaturated urethane B-3 is synthesized and unsaturated urethane resin b-
Preparation of 3 was performed.

Synthesis of unsaturated urethane B-4 and preparation of unsaturated urethane resin b-4 2,4-Tolylene diisocyanate 87 parts (0.5 mol), methyl methacrylate 249 parts (2.49 mol)
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-4 containing 60% of unsaturated urethane B-4 and 40% of methyl methacrylate.

Preparation of unsaturated urethane resin r-5 In the preparation of unsaturated urethane resin b-1, the same as the preparation of unsaturated urethane resin b-1 except that the amount of neopentyl glycol diacrylate used was 37 parts. The unsaturated urethane resin r- containing 90% of unsaturated urethane B-1 and 10% of neopentyl glycol diacrylate.
5 was prepared.

Preparation of unsaturated urethane resin r-6 Dissolve 6 parts of unsaturated urethane resin b-1 and 94 parts of neopentyl glycol diacrylate to dissolve 3% of unsaturated urethane B-1 and neopentyl. An unsaturated urethane resin r-6 containing 97% of glycol diacrylate was prepared.

Preparation of unsaturated urethane resin r-7 In the preparation of unsaturated urethane resin b-4, the procedure of preparation of unsaturated urethane resin b-4 was repeated except that the amount of methyl methacrylate used was 41 parts. Unsaturated urethane B-
An unsaturated urethane resin r-7 containing 90% of 4 and 10% of methyl methacrylate was prepared.

Preparation of unsaturated urethane resin r-8 Unsaturated urethane resin B-4 was mixed with 5 parts of unsaturated urethane resin b-4 and dissolved in 95 parts of methyl methacrylate to dissolve 3 parts of unsaturated urethane resin B-4.
% And 97% methylmethacrylate were used to prepare an unsaturated urethane resin r-8.

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

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

Preparation of unsaturated urethane resin r-9 Preparation of unsaturated urethane resin c-2 except that the amount of diethoxylated bisphenol A diacrylate used was 68 parts in the preparation of unsaturated urethane resin c-2. Similarly, an unsaturated urethane resin r-9 containing 90% of unsaturated urethane C-2 and 10% of diethoxylated bisphenol A diacrylate was prepared.

Preparation of unsaturated urethane resin r-10: 6 parts of unsaturated urethane resin c-2 and 94 parts of diethoxylated bisphenol A diacrylate are mixed and dissolved,
An unsaturated urethane resin r-10 containing 3% of unsaturated urethane C-2 and 97% of diethoxylated bisphenol A diacrylate was prepared.

[0064]

[Table 1]

[0065]

[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 * 4: Diethoxylated bisphenol A diacrylate ** 1: Glycerin monoacrylate monooctanoate ** 2: Glycerin monomethacrylate monooctanoate ** 3: Glycerin monomethacrylate / monoisopalmitate ** 4: Diethylene glycol monomethacrylate ** 5: Glycerin diacrylate ** 6: Hydroxyethyl acrylate ** 7: 2,4-Tolylene diisocyanate ** 8: Polypropylene glycol (Average molecular weight 40
0) / 2,4-tolylene diisocyanate (NCO group average 2) = 1/2 (molar ratio) Reactant ** 9: Isophorone diisocyanate

Test Category 3 (Production of Crosslinked Polymer Particles) Crosslinked polymer particles Pa-1 to Pa-4, Pb-1 to Pb-
4, Pc-1, Pc-2, Pr-1 to Pr-10 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. After stirring, the temperature was raised to 70 ° C., and the mixture was kept at 70 to 80 ° C. for 6 hours to carry out radical polymerization, then 10 parts of a 1% aqueous solution of hydroquinone was added as a polymerization inhibitor to stop the polymerization reaction, and stirring was continued. Was continued and cooled to room temperature. Next, 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 were filtered off, and the washing and filtration were repeated until the washing water became neutral, and the particles were dried to obtain crosslinked polymer particles Pa-1.
The crosslinked polymer particles Pa-1 obtained here have an average particle diameter of 1
The particles were spherical particles of 5 μm.

Examples 2 to 4 and Comparative Examples 1 to 4 (crosslinked polymer particles Pa-2 to Pa-4 and Pr by 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 5 (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. After stirring, the temperature was raised to 70 ° C, and the temperature was maintained at 70 to 80 ° C for 4 hours to carry out radical polymerization. Then, 10 parts of a 1% aqueous solution of hydroquinone was added as a polymerization inhibitor to stop the polymerization reaction, and stirring was continued. Was continued and cooled to room temperature. Next, 100 parts of a 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 have an average particle diameter of 0.7.
It was a spherical particle of μm.

Examples 6 to 10 and Comparative Examples 5 to 10 (crosslinked polymer particles Pb-2 to Pb-4, P by emulsion polymerization method)
Production of c-1, Pc-2 and Pr-5 to Pr-10) 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.

Comparative Examples 11 to 13 (Test for Decreasing Unreacted Radical Polymerizable Group in Crosslinked Polymer Particles by Heat Treatment) Crosslinked polymer particles Pa− obtained in Examples 1, 5 and 9
1, Pb-1 and Pc-1 were post-cured at 150 ° C. for 12 hours to obtain Pa-1H, Pb-1H and Pc-1H as heat-treated crosslinked polymer particles. 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.

The solubility of each of the crosslinked polymer particles obtained above 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.

In each of the crosslinked polymer particles obtained above, the ratio of the unreacted radical polymerizable groups remaining in the crosslinked polymer particles to the total radical polymerizable groups contained in the unsaturated urethane resin used as the raw material. Was calculated by the following method. The results are shown in Table 4. ..Calculation method of ratio of unreacted radically polymerizable group: Perkin Elmer 176 for the unsaturated urethane resin used for preparing the crosslinked polymer particles and the obtained crosslinked polymer particles
Using 0X type FT-IR, measuring the area ratio of the absorption spectrum at a wave number 1640 cm ^-1 attributable to wavenumber 1740 cm ^-1 and olefinic double bonds attributable to the ester carbonyl group by KBr method, was calculated by the following formula . Unreacted radically polymerizable group ratio (%) = (A ₁ / A ₀ ).
× 100 A _0: crosslinked polymer area ratio in the 1640 cm ^-1 / 1740 cm ^-1 unsaturated urethane resin used in the preparation of the particles A _1: area ratio of the 1640 cm ^-1 / 1740 cm ^-1 of the crosslinked polymer particles

[0075]

[Table 3]

[0076]

[Table 4]

Test Category 4 (Preparation of Composition and Curing Molding by Optical Stereolithography and Evaluation of Cured Molded Product) Examples 11 to 22 and Comparative Examples 14 to 35 (Preparation of Composition) Tables as materials used 5 or 100 parts by weight of the unsaturated urethane resin shown in Table 6, 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 or other particles shown in Table 5 or Table 6 in a mixing container at a ratio shown in Table 5 or Table 6 and uniformly using a paint shaker. An unsaturated urethane resin composition was prepared by stirring and mixing until it became. In Comparative Examples 33 to 35,
The thermoplastic polymer was used by uniformly dissolving it in 100 parts by weight of the unsaturated urethane resin in the proportion shown in Table 6.

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 5 and 6.

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.

[0080]

[Table 5]

[0081]

[Table 6]

In Tables 5 and 6, a-1, a-2, a-3, b-1, b-2, b-3, c
-1, c-2: Unsaturated urethane resin Pa-1, Pa-2, Pa-3, Pb-1, Pb-2, prepared in Test Category 2
Pb-3, Pc-1, Pc-2, Pr-1, Pr-2,
Pr-5, Pr-6, Pr-9, Pr-10, Pa-1
H, Pb-1H, Pc-1H: Crosslinked polymer particles produced in Test Category 3 * 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 Method Using These and Evaluation of Cured Molding) Examples 23 to 28 and Comparative Examples 36 to 45 (Preparation of Composition) As materials to be used Unsaturated urethane resin 100 shown below
By weight, 1 part by weight of methyl ethyl ketone peroxide as a radical polymerization initiator, and 0.0075 parts by weight of cobalt naphthenate as a curing accelerator were 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 7.

· 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

[0086]

[Table 7]

[0087]

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-7- 228648 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 299/00-299/08 C08F 290/00-290/14 C08G 18/67

Claims (14)

(57) [Claims] 1. Crosslinked polymer particles obtained by radically polymerizing the following unsaturated urethane resin, wherein 5 to 60 mol% of all radically polymerizable groups contained in the unsaturated urethane resin.
An unsaturated urethane resin modifier for curing molding, comprising a cross-linked polymer particle containing the radical-polymerizable group as described above as an unreacted radical-polymerizable group. Unsaturated urethane resin: One or more unsaturated monools selected from the unsaturated monools represented by the following formula 1 and the unsaturated monools represented by the following formula 2 and the diisocyanate compound are unsaturated. The unsaturated urethane obtained by the urethanization reaction at a ratio of monool / the diisocyanate compound = 2/1 (molar ratio) and the (meth) acrylic acid ester copolymerizable with the unsaturated urethane are the unsaturated compounds. Urethane / (meth) acrylic acid ester = 80
An unsaturated urethane resin having a ratio of / 20 to 20/80 (weight ratio). [Formula 1] [Formula 2] [In Formula 1 and Formula 2, Y ¹ is a residue Y ² from a divalent or trivalent polyol selected from polyhydric alcohols, polyether polyols, polyester polyols and polyether ester polyols; Residues excluding hydroxyl group R ¹ , R ² : H or CH ₃ R ³ : aliphatic hydrocarbon group having 5 to 21 carbon atoms m: 1 or 2] 2. The curable molding according to claim 1, wherein the unsaturated urethane constituting the unsaturated urethane resin is obtained by subjecting an unsaturated monool having an acryloxy group in the molecule to a diisocyanate compound in a urethane reaction. Unsaturated urethane resin modifier. 3. An unsaturated urethane resin is constituted (meth).
The unsaturated urethane resin for curing and molding according to claim 1 or 2, wherein the acrylic acid ester is an acrylic acid ester of a divalent to tetravalent polyol selected from alcohols, polyether polyols, polyester polyols, polyether ester polyols and alkoxylated bisphenols. Modifier. 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 modifier according to claim 1, 2, 3, 4 or 5 is added in an amount of 30 to 100 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 unsaturated monools selected from unsaturated monools represented by the following formula 3 and unsaturated monools represented by the following formula 4 and the diisocyanate compound are unsaturated. The unsaturated urethane obtained by urethanization reaction at a ratio of monool / the diisocyanate compound = 2/1 (molar ratio) and the (meth) acrylic acid ester copolymerizable with the unsaturated urethane are the unsaturated compounds. Urethane / (meth) acrylic acid ester = 80
An unsaturated urethane resin having a ratio of / 20 to 20/80 (weight ratio). [Formula 3] [Formula 4] [In Formula 3 and Formula 4, Y ³ is a residue Y ⁴ from a divalent or trivalent polyol selected from polyhydric alcohols, polyether polyols, polyester polyols and polyether ester polyols; residues R ⁴ excluding a hydroxyl group, R ^5: H or CH ₃ R ^6: aliphatic hydrocarbon group of 5 to 21 carbon atoms n: 1 or 2] 8. The curable molding according to claim 7, wherein the unsaturated urethane constituting the unsaturated urethane resin is obtained by subjecting an unsaturated monool having an acryloxy group in the molecule to a diisocyanate compound in a urethane reaction. Unsaturated urethane resin composition. 9. An unsaturated urethane resin is constituted (meth).
The unsaturated urethane resin for curing and molding according to claim 7 or 8, wherein the acrylic acid ester is an acrylic acid ester of a divalent to tetravalent polyol selected from alcohols, polyether polyols, polyester polyols, polyether ester polyols and alkoxylated bisphenols. Composition. 10. The unsaturated urethane constituting the unsaturated urethane resin is an unsaturated urethane obtained from an unsaturated monool represented by formula 3 and a diisocyanate compound, and the unsaturated urethane forming a modifier is obtained. The unsaturated urethane resin composition for curing and molding according to claim 7, 8 or 9, wherein the unsaturated urethane constituting the saturated urethane resin is an unsaturated urethane obtained from an unsaturated monool represented by formula 1 and a diisocyanate compound. 11. An unsaturated urethane constituting an unsaturated urethane resin is an unsaturated urethane obtained from an unsaturated monool represented by the formula 4 and a diisocyanate compound, and is an unsaturated urethane which forms a modifier. The unsaturated urethane resin composition for curing and molding according to claim 7, 8 or 9, wherein the unsaturated urethane constituting the saturated urethane resin is an unsaturated urethane obtained from an unsaturated monool represented by formula 2 and a diisocyanate compound. 12. The unsaturated urethane constituting the unsaturated urethane resin is an unsaturated urethane obtained from an unsaturated monool represented by formula 3 and an unsaturated monool represented by formula 4 and a diisocyanate compound, and The unsaturated urethane constituting the unsaturated urethane resin that forms the modifier is an unsaturated monool represented by the formula 1 or an unsaturated urethane obtained from the unsaturated monool represented by the formula 2 and a diisocyanate compound. Claim 7, 8 or 9
The unsaturated urethane resin composition for curing and molding described above. 13. When the unsaturated urethane resin composition for curing and molding according to claim 6, 7, 8, 9, 10, 11 or 12 is cured and molded, an unsaturated urethane resin and a modifier are polymerized to react with each other. A method for curing and molding an unsaturated urethane resin composition for curing and molding, which is characterized by forming an integrally molded product. 14. When curing and molding the unsaturated urethane resin composition for curing and molding according to claim 8, 9, 10, 11 or 12, by polymerizing an unsaturated urethane resin and a modifier. A method for curing and molding an unsaturated urethane resin composition for curing and molding, which is characterized as an integrally molded product.