JP2015021044A - Photocurable resin composition for forming cured product having excellent heat resistance and dimensional accuracy - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethanated acrylic compound-containing photocurable resin composition for forming a photocured product having less shrinkage at photocuring, and having excellent heat resistance, hardness, scratch resistance, and mechanical characteristics.SOLUTION: A photocurable resin composition comprises a urethanated acrylic compound represented by the general formula (I) where A is epoxy (meth) acrylate residue, and a photoradical polymerization initiator.

Description

The present invention relates to a photocurable resin composition containing a specific urethane-modified acrylic compound, an unprecedented novel urethane-modified acrylic compound used for the photocurable resin composition, and a method for producing the same.
More specifically, the present invention relates to a photocurable resin composition containing a novel urethanized acrylic compound having 3 or more (meth) acryloyloxy groups, and a novel urethanized acrylic used for the photocurable resin composition. The photocurable resin composition of the present invention is a liquid at room temperature and has excellent handleability, and can form a photocured product with small shrinkage during photocuring and excellent dimensional accuracy. In addition, a cured product obtained by photocuring the photocurable resin composition of the present invention is excellent in heat resistance, hardness, mechanical properties and the like, and can be effectively used for various applications.

Photocurable resins are widely used for various applications such as coating materials such as hard coats, photoresists, molded articles and three-dimensionally shaped objects.
The urethanized acrylic compound is one of typical photocurable resins, and shrinks during photocuring even for photocurable resin compositions containing a urethanized acrylic compound as the application expands. The cured product obtained by photocuring is required to have excellent heat resistance, hardness, mechanical properties, and the like.

As a urethanized acrylic compound-containing photocurable resin composition that forms a photocured product with improved heat resistance, a photocurable resin composition containing a urethanized acrylic compound into which an isocyanurate ring is introduced (Patent Document 1). By increasing the number of (meth) acrylic groups in the urethanized acrylic compound, the double bond concentration of the photocurable resin composition is increased to increase the crosslink density of the cured product obtained by the photocuring reaction. (Patent Documents 2 and 3) are known which improve the heat resistance and hardness of the resin.
In the case of these conventional techniques, the heat resistance of the photocured product is improved, but the shrinkage during photocuring tends to be large, and in particular, the double bond concentration in the photocurable resin composition is increased to increase the crosslinking density. When the heat resistance is improved, the shrinkage at the time of photocuring is increased and the dimensional accuracy of the photocured product is reduced, and when the photocured product is a film, the adhesion with the base material is poor. It was easy to occur.

  Under such circumstances, the present inventors synthesized an unprecedented novel urethanized acrylic compound and prepared a photocurable resin composition using the urethanized acrylic compound. The composition has a small shrinkage during photocuring and can form a photocured product with excellent dimensional accuracy, and the cured product obtained by photocuring has excellent heat resistance (Patent Document 4).

  With the expansion of applications of photo-curable resin compositions and the advancement and diversification of the required physical properties of photo-curable resin compositions, heat resistance can also be applied to urethane-modified acrylic compounds and photo-curable resin compositions containing them. Various photocurable resin compositions having various properties such as properties, low shrinkage upon photocuring, and high hardness are demanded.

JP-A-6-128342 JP-A-9-227640 JP 2000-204125 A Japanese Patent No. 4021347

The object of the present invention is to form a photocured material that is liquid at room temperature, has excellent handling properties, has small shrinkage during photocuring and has excellent dimensional accuracy, and has excellent heat resistance, high hardness, and excellent scratch resistance. Another object of the present invention is to provide a urethanized acrylic compound-containing photocurable resin composition that can form a photocured product having excellent mechanical properties.
And the objective of this invention is providing the urethanization acrylic compound effective in preparation of the said photocurable resin composition, and its manufacturing method.

  In order to achieve the above-mentioned object, the present inventors have made researches and, as part of this, have produced a new urethanized acrylic compound which has not been obtained conventionally. And when the photocurable resin composition was prepared using the novel urethanized acrylic compound, and the photocurable resin composition was photocured to form a cured product, the photocurable resin composition was It is liquid at room temperature and has excellent handleability. It can form a photocured product with small shrinkage during photocuring and excellent dimensional accuracy, and it can be obtained by photocuring the photocurable resin composition. Discovered that the product has high heat distortion temperature and excellent heat resistance, excellent adhesion to various base materials, firmly adheres to various base materials, high hardness, and is not easily damaged. The present invention has been completed based on the above.

That is, the present invention
(1) the following general formula (I);

［式中、Ｒ¹およびＲ²はそれぞれ独立して水素原子またはメチル基、Ｒ³は水素原子または炭素数１〜４のアルキル基、Ａは１個以上のグリシジルエーテル基を有し、水酸基を有するかまたは有しないグリシジルエーテル型エポキシ化合物にアクリル酸およびメタクリル酸の一方または両方を反応させて得られたエポキシ（メタ）アクリレート体から、グリシジル基と（メタ）アクリル酸との反応により生成した構造部分およびイソシアネート基と反応した水酸基部分を除いた残基、Ｄはジイソシアネート残基またはトリイソシアネート残基、Ｅは直接結合または２価の脂肪族炭化水素基を示し、ａは１、２または３、ｂは１または２、ｄは０、１、２、３または４、ｅは０、１、２、３または４、ｆは０、１、２、３または４であって且つｄとｅの合計が２、３または４であり、ｄとｆの合計が１以上の整数である。］
で表されるウレタン化アクリル化合物（Ｉ）および光ラジカル重合開始剤を含有することを特徴とする光硬化性樹脂組成物である。

Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A has one or more glycidyl ether groups, Structure formed by reaction of glycidyl group and (meth) acrylic acid from epoxy (meth) acrylate body obtained by reacting one or both of acrylic acid and methacrylic acid with or without glycidyl ether type epoxy compound A moiety and a residue excluding the hydroxyl group reacted with an isocyanate group, D is a diisocyanate residue or a triisocyanate residue, E is a direct bond or a divalent aliphatic hydrocarbon group, a is 1, 2 or 3, b is 1 or 2, d is 0, 1, 2, 3 or 4, e is 0, 1, 2, 3 or 4, f is 0, 1, 2, 3 or 4 and The sum of e is 2, 3 or 4, the sum of d and f is an integer of 1 or more. ]
The photocurable resin composition characterized by containing the urethane-ized acrylic compound (I) represented by these, and radical photopolymerization initiator.

And this invention,
(2) The photocurable resin composition according to (1), further including a radical polymerizable compound (II) other than the urethanized acrylic compound (I).

The present invention also provides:
(3) A in the above general formula (I) is an epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with a glycidyl group of an aliphatic diol monoglycidyl ether; two glycidyls of an aliphatic diol diglycidyl ether Epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with each of the groups; Epoxy (meth) acrylate body in which glycidyl group of aliphatic triol monoglycidyl ether is reacted with (meth) acrylic acid; Aliphatic triol diglycidyl ether An epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with two glycidyl groups of the above; an epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with three glycidyl groups of an aliphatic triol triglycidyl ether; Aliphatic tetraol monoglycidylate (Meth) acrylates in which (meth) acrylic acid is reacted with the glycidyl group of ruthenium; epoxy (meth) acrylates in which (meth) acrylic acid is reacted with the two glycidyl groups of the aliphatic tetraol diglycidyl ether; Epoxy (meth) acrylate in which (meth) acrylic acid has reacted with three glycidyl groups of aliphatic tetraol triglycidyl ether; (meth) acrylic acid has reacted with four glycidyl groups of aliphatic tetraol tetraglycidyl ether Epoxy (meth) acrylate body; epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with glycidyl group of aliphatic pentaol monoglycidyl ether; (meth) on two glycidyl groups of aliphatic pentaol diglycidyl ether Epoxy (meth) acrylate reacted with acrylic acid Relate body: Epoxy (meth) acrylate body in which (meth) acrylic acid was reacted with 3 glycidyl groups of aliphatic pentaol triglycidyl ether; (meth) acrylic group on 4 glycidyl groups of aliphatic pentaol tetraglycidyl ether Epoxy (meth) acrylate body reacted with acid; epoxy (meth) acrylate body reacted with (meth) acrylic acid on 5 glycidyl groups of aliphatic pentaol pentaglycidyl ether; glycidyl group of aliphatic hexaol monoglycidyl ether (Meth) acrylate reacted with (meth) acrylic acid; epoxy (meth) acrylate reacted with (meth) acrylic acid on two glycidyl groups of aliphatic hexaol diglycidyl ether; aliphatic hexaol tri 3 pieces of glycidyl ether Epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with glycidyl group; Epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with four glycidyl groups of aliphatic hexaol tetraglycidyl ether; Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with five glycidyl groups of all pentaglycidyl ether; Epoxy ((meth) acrylic acid is reacted with six glycidyl groups of aliphatic hexaol hexaglycidyl ether) The above (1), which is a residue obtained by removing from the epoxy (meth) acrylate body selected from the (meth) acrylate body, the structure portion formed by the reaction of glycidyl group and (meth) acrylic acid and the hydroxyl group portion reacted with the isocyanate group. Or it is the photocurable resin composition of (2).
The present invention also provides:
(4) The photocurable resin composition according to any one of (1) to (3), wherein D is an isocyanurate residue that is a trimer of a diisocyanate compound; and
(5) The light according to (4), wherein the isocyanurate residue is an isocyanurate residue of isophorone diisocyanate, an isocyanurate residue of hexamethylene diisocyanate, or an isocyanurate residue of methylenebis (cyclohexanediyl) diisocyanate. Curable resin composition;
It is.

Furthermore, the present invention provides
(6) The following general formula (I)

［式中、Ｒ¹およびＲ²はそれぞれ独立して水素原子またはメチル基、Ｒ³は水素原子または炭素数１〜４のアルキル基、Ａは１個以上のグリシジルエーテル基を有し、水酸基を有するかまたは有しないグリシジルエーテル型エポキシ化合物にアクリル酸およびメタクリル酸の一方または両方を反応させて得られたエポキシ（メタ）アクリレート体から、グリシジル基と（メタ）アクリル酸との反応により生成した構造部分およびイソシアネート基と反応した水酸基部分を除いた残基、Ｄはジイソシアネート残基またはトリイソシアネート残基、Ｅは直接結合また２価の脂肪族炭化水素基を示し、ａは１、２または３、ｂは１または２、ｄは０、１、２、３または４、ｅは０、１、２、３または４、ｆは０、１、２、３または４であって且つｄとｅの合計が２、３または４であり、ｄとｆの合計が１以上の整数である。］
で表されるウレタン化アクリル化合物（Ｉ）である。

Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A has one or more glycidyl ether groups, Structure formed by reaction of glycidyl group and (meth) acrylic acid from epoxy (meth) acrylate body obtained by reacting one or both of acrylic acid and methacrylic acid with or without glycidyl ether type epoxy compound A moiety and a residue excluding a hydroxyl group reacted with an isocyanate group, D is a diisocyanate residue or a triisocyanate residue, E is a direct bond or a divalent aliphatic hydrocarbon group, a is 1, 2 or 3, b is 1 or 2, d is 0, 1, 2, 3 or 4, e is 0, 1, 2, 3 or 4, f is 0, 1, 2, 3 or 4 and d Total e is 2, 3 or 4, the sum of d and f is an integer of 1 or more. ]
Is a urethanized acrylic compound (I).

And this invention,
(7) the following general formula (ia);

（式中、Ｒ¹は水素原子またはメチル基、Ｒ³は水素原子または炭素数１〜４のアルキル基、Ｅは直接結合または２価の脂肪族炭化水素基を示し、ａは１、２または３である。］
で表される水酸基含有（メタ）アクリレート化合物(ｉ−ａ)と、下記の一般式(ｉ−ｂ)；

Wherein R ¹ is a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, E is a direct bond or a divalent aliphatic hydrocarbon group, and a is 1, 2 or 3.]
A hydroxyl group-containing (meth) acrylate compound (ia) represented by the following general formula (ib);

（式中、Ｄはジイソシアネート残基またはトリイソシアネート残基を示し、ｂは１または２である。）
で表されるポリイソシアネート化合物（ｉ−ｂ）を反応させて、下記の一般式(ｉ−ｃ)；

(In the formula, D represents a diisocyanate residue or a triisocyanate residue, and b is 1 or 2.)
And a polyisocyanate compound (ib) represented by the following general formula (ic):

（式中、Ｒ¹は水素原子またはメチル基、Ｒ³は水素原子または炭素数１〜４のアルキル基、Ｄはジイソシアネート残基またはトリイソシアネート残基、Ｅは直接結合または２価の脂肪族炭化水素基を示し、ａは１、２または２、ｂは１または２である。）
で表されるイソシアネート基含有ウレタン化アクリル化合物（ｉ−ｃ）をつくり、当該イソシアネート基含有ウレタン化アクリル化合物（ｉ−ｃ）を、１個以上のグリシジルエーテル基を有し、水酸基を有するかまたは有しないグリシジルエーテル型エポキシ化合物にアクリル酸および／またはメタクリル酸を反応させて得られた下記の一般式（ｉ−ｄ）；

(Wherein R ¹ is a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, D is a diisocyanate residue or triisocyanate residue, E is a direct bond or divalent aliphatic carbonization) Represents a hydrogen group, a is 1, 2 or 2, and b is 1 or 2.)
Or an isocyanate group-containing urethanized acrylic compound (ic) represented by the formula: wherein the isocyanate group-containing urethanized acrylic compound (ic) has one or more glycidyl ether groups and a hydroxyl group or The following general formula (id) obtained by reacting acrylic acid and / or methacrylic acid with a glycidyl ether type epoxy compound which does not have;

［式中、Ｒ²は水素原子またはメチル基、Ａは１個以上のグリシジルエーテル基を有し、水酸基を有するかまたは有しないグリシジルエーテル型エポキシ化合物にアクリル酸および／またはメタクリル酸を反応させて得られたエポキシ（メタ）アクリレート体からグリシジル基と（メタ）アクリル酸との反応により生成した構造部分および水酸基部分を除いた残基を示し、ｅは０、１、２、３または４、ｇは１〜８の整数である。］
で表されるエポキシ（メタ）アクリレート（ｉ−ｄ）と反応させて、下記の一般式(Ｉ)；

[Wherein R ² represents a hydrogen atom or a methyl group, A represents one or more glycidyl ether groups, and a glycidyl ether type epoxy compound having or not having a hydroxyl group is reacted with acrylic acid and / or methacrylic acid. The residue obtained by removing the structural part and the hydroxyl part produced by the reaction of a glycidyl group and (meth) acrylic acid from the obtained epoxy (meth) acrylate body, e is 0, 1, 2, 3 or 4, g Is an integer of 1-8. ]
Is reacted with an epoxy (meth) acrylate (id) represented by the following general formula (I):

［式中、Ｒ¹およびＲ²はそれぞれ独立して水素原子またはメチル基、Ｒ³は水素原子または炭素数１〜４のアルキル基、Ａは１個以上のグリシジルエーテル基を有し、水酸基を有するかまたは有しないグリシジルエーテル型エポキシ化合物にアクリル酸およびメタクリル酸の一方または両方を反応させて得られたエポキシ（メタ）アクリレート体から、グリシジル基と（メタ）アクリル酸との反応により生成した構造部分およびイソシアネート基と反応した水酸基部分を除いた残基、Ｄはジイソシアネート残基またはトリイソシアネート残基、Ｅは直接結合または２価の脂肪族炭化水素基を示し、ａは１、２または３、ｂは１または２、ｄは０、１、２、３または４、ｅは０、１、２、３または４、ｆは０、１、２、３または４であって且つｄとｅの合計が２、３または４であり、ｄとｆの合計が１以上の整数である。］
で表されるウレタン化アクリル化合物（Ｉ）を製造する方法。
方法である。

Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A has one or more glycidyl ether groups, Structure formed by reaction of glycidyl group and (meth) acrylic acid from epoxy (meth) acrylate body obtained by reacting one or both of acrylic acid and methacrylic acid with or without glycidyl ether type epoxy compound A moiety and a residue excluding the hydroxyl group reacted with an isocyanate group, D is a diisocyanate residue or a triisocyanate residue, E is a direct bond or a divalent aliphatic hydrocarbon group, a is 1, 2 or 3, b is 1 or 2, d is 0, 1, 2, 3 or 4, e is 0, 1, 2, 3 or 4, f is 0, 1, 2, 3 or 4 and The sum of e is 2, 3 or 4, the sum of d and f is an integer of 1 or more. ]
A process for producing a urethanized acrylic compound (I) represented by the formula:
Is the method.

The urethane-modified acrylic compound (I) of the present invention has three or more (meth) acryloyloxy groups as shown in the general formula (I), and the three or more (meth) acryloyloxy groups. Is not present only at the molecular end, and a part of three or more (meth) acryloyloxy groups are close to the group A without a urethane bond [the center of the urethanized acrylic compound (I) molecule The remaining (meth) acryloyloxy group is present at the molecular end of the urethanized acrylic compound (I) via a urethane bond, and is polymerizable (crosslinkable) (meth) acryloyloxy. The groups are distributed throughout the urethanized acrylic compound (I) molecule.
Therefore, when the photocurable resin composition of the present invention containing the urethanized acrylic compound (I) is photocured, a crosslinked structure (polymerized structure) in which the crosslinking points are uniformly or almost uniformly distributed throughout the cured product is formed. Therefore, it is possible to form a photocured product (photocured film, molded product, three-dimensional modeled product, etc.) having a small shrinkage at the time of photocuring and excellent in dimensional accuracy, and the photocured product obtained thereby is localized. There are no defects and the uniformity of the physical properties of the entire photocured product is excellent, along with this, it has a high heat distortion temperature, excellent heat resistance, high hardness, excellent scratch resistance, and mechanical properties. Is also excellent.

The urethanized acrylic compound (I) of the present invention is excellent in handleability because it is liquid at room temperature (25 ° C.), and is a non-solvent type containing no organic solvent using the urethanized acrylic compound (I). Both a photocurable resin composition and a solvent-type photocurable resin composition containing an organic solvent can be prepared.
The cured film formed from the photocurable resin composition of the present invention containing the urethanized acrylic compound (I) has excellent adhesion to various base materials, adheres firmly to various base materials, and has high hardness. It has excellent scratch resistance, weather resistance, and is unlikely to cause yellowing or other discoloration.

The present invention is described in detail below.
The urethanized acrylic compound (I) used in the photocurable resin composition of the present invention is represented by the following general formula (I), and includes three acryloyloxy groups and / or methacryloyloxy groups per molecule in total. Have more.
In the urethanized acrylic compound (I), as shown in the following general formula (I), some (meth) acryloyloxy groups out of three or more (meth) acryloyloxy groups are urethane bonded via a urethane bond. The remaining (meth) acryloyloxy group is bonded to the molecular end of the fluorinated acrylic compound (I), and forms oxygen in the form of a structural portion formed by the reaction of glycidyl group and (meth) acrylic acid without via a urethane bond. It is directly bonded to residue A through an atom.

In the above general formula (I), R ¹ and R ² are each independently a hydrogen atom or a methyl group. In the above general formula (I), when R ³ is a hydrogen atom, E is a direct bond, and a is 2, both of two R ¹ are methyl groups or two R ¹ One is preferably a hydrogen atom and the other is a methyl group. In R ³ is a hydrogen atom, E is urethane acrylate compound a is 2 direct bond (I) is manufactured using a glycerin di (meth) acrylate as the starting compound, glycerin diacrylate (for R ¹ It is preferable not to use since both of them are carcinogenic and skin irritating toxic substances. This is because ^one of R ¹ is a hydrogen atom and the other is a methyl group, or both of R ¹ Is preferably a methyl group. When di (meth) acrylate other than glycerin di (meth) acrylate is used (when the figure is 2), two R ^{1 s} are both hydrogen atoms, both methyl groups, or one is hydrogen. Either atom or the other may be a methyl group.
In the general formula (I), R ³ is a hydrogen atom or a carbon number of 1 to 4 (specifically, a methyl group, an ethyl group, a propyl group, or a butyl group), and is a hydrogen atom, a methyl group, or an ethyl group. Is preferable from the viewpoint of ease of synthesis.

In the above general formula (I), A is obtained by reacting one or both of acrylic acid and methacrylic acid with a glycidyl ether type epoxy compound having one or more glycidyl ether groups and having or not having a hydroxyl group. The residue (remaining part) excluding the structure part produced | generated by reaction of a glycidyl group and (meth) acrylic acid from the obtained epoxy (meth) acrylate body, and the hydroxyl group part which reacted with the isocyanate group is shown.
In the above general formula (I), the above-mentioned “structure portion formed by the reaction of glycidyl group and (meth) acrylic acid” in the epoxy (meth) acrylate body is the above general formula (I). Among the three types of groups (upper, middle and lower groups) bonded to the residue A, the upper group [a group in which a (meth) acryloyloxy group is bonded to the terminal via a urethane bond] A structural part represented by the formula “—O—CH ₂ —CH {—CH ₂ —O—CO—C (R ² ) ═CH ₂ } —O—” adjacent to the residue A and a lower group [ie refers to the formula _{"-O-CH 2 -CH (OH)} -CH 2 -O-CO-C (R 2) = structure represented by CH _2" which is directly bonded to residue a.
In the above general formula (I), the above-mentioned “hydroxyl moiety reacted with an isocyanate group” in the epoxy (meth) acrylate body means the group “A— O— CO” in the middle stage in the above general formula (I). -NH-D -... "represents an oxygen atom part indicated by an underline (the oxygen atom part on the left side in the above general formula (I) that reacts with an isocyanate group to form a urethane bond). Say.

Residue A may have an unreacted glycidyl group or other epoxy group in the group, but it does not have an unreacted epoxy group in the synthesis of the urethanized acrylic compound (I). From the viewpoints of ease, hardness of the cured film, long-term storage stability, and the like. Therefore, in the above general formula (I), the residue A is represented by the following general formula (ie):
(G) g-A '-(OH) e (ie)
(In the formula, A ′ is a residue excluding an epoxy group such as a glycidyl group in an epoxy compound, G is a glycidyloxy group, e is 0, 1, 2, 3 or 4, and g is an integer of 1-8. Show.)
All of the glycidyl groups (g glycidyl groups) of the glycidyl ether type epoxy compound having 1 to 8 glycidyl groups and having 0 to 4 hydroxyl groups are reacted with (meth) acrylic acid. It is preferable that it is the residue A 'of the epoxy (meth) acrylate body which forms the (meth) acrylic acid ester bond.
The glycidyl ether type epoxy compound represented by the above general formula (ie) for forming an epoxy (meth) acrylate body is a urethanized acrylic compound (I) that is liquid at room temperature. A monoglycidyl ether or polyglycidyl ether of an aliphatic polyol is preferred.
A urethanized acrylic compound obtained by using an epoxy (meth) acrylate formed from a glycidyl ether of an aromatic polyol has a too high viscosity or a solid state at room temperature, and is inferior in handleability.

  Although not limited, As a specific example of the residue A in said general formula (I), the epoxy (meth) acrylate body which (meth) acrylic acid reacted with the glycidyl group of aliphatic diol monoglycidyl ether; Epoxy (meth) acrylates in which (meth) acrylic acid is reacted with each of the two glycidyl groups of the aliphatic diol diglycidyl ether; epoxy (meth) acrylic acid is reacted with the glycidyl group of the aliphatic triol monoglycidyl ether ( (Meth) acrylate body; epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with each of two glycidyl groups of aliphatic triol diglycidyl ether; each of three glycidyl groups of aliphatic triol triglycidyl ether Epoxy reacted with (meth) acrylic acid ) Acrylate body; epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with glycidyl group of aliphatic tetraol monoglycidyl ether; (meth) acrylic group on each of two glycidyl groups of aliphatic tetraol diglycidyl ether Epoxy (meth) acrylate body reacted with acid; epoxy (meth) acrylate body reacted with (meth) acrylic acid on each of the three glycidyl groups of aliphatic tetraol triglycidyl ether; aliphatic tetraol tetraglycidyl ether An epoxy (meth) acrylate body in which (meth) acrylic acid has reacted with each of the four glycidyl groups; an epoxy (meth) acrylate body in which (meth) acrylic acid has reacted with a glycidyl group of an aliphatic pentaol monoglycidyl ether; Group pentaol (Meth) acrylic acid reacted with each of the two glycidyl groups of glycidyl ether; (meth) acrylic acid reacted with each of the three glycidyl groups of aliphatic pentaol triglycidyl ether Epoxy (meth) acrylate body; epoxy (meth) acrylate body in which (meth) acrylic acid reacts with each of the four glycidyl groups of aliphatic pentaol tetraglycidyl ether; five glycidyl of aliphatic pentaol pentaglycidyl ether Epoxy (meth) acrylate body in which (meth) acrylic acid has reacted with each of the groups; Epoxy (meth) acrylate body in which (meth) acrylic acid has reacted with the glycidyl group of aliphatic hexaol monoglycidyl ether; Aliphatic hexaol di Of glycidyl ether Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with each of two glycidyl groups; epoxy (meth) acrylic acid is reacted with each of three glycidyl groups of aliphatic hexaol triglycidyl ether ) Acrylate body; epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with each of four glycidyl groups of aliphatic hexaol tetraglycidyl ether; each of five glycidyl groups of aliphatic hexaol pentaglycidyl ether Epoxy (meth) acrylate body reacted with (meth) acrylic acid; epoxy selected from epoxy (meth) acrylate body reacted with (meth) acrylic acid on each of the six glycidyl groups of aliphatic hexaol hexaglycidyl ether (Meth) acrylate body , And the like residue obtained by removing the hydroxyl moieties reacted with the resulting structure portion and isocyanate groups by reaction with glycidyl groups and (meth) acrylic acid.

  Among them, the residue A is a linear or branched saturated aliphatic hydrocarbon group, and the acquisition of a raw material compound [particularly a glycidyl ether type epoxy compound] for producing the urethanized acrylic compound (I) Easiness, ease of synthesis of urethanized acrylic compound (I), viscosity and handleability of photocurable resin composition containing urethanized acrylic compound (I), photocuring containing urethanized acrylic compound (I) It is preferable from the viewpoints of the shrinkage prevention property at the time of photocuring the curable resin composition, the dimensional accuracy of the cured product obtained by photocuring the photocurable resin composition, heat resistance, mechanical properties, hardness and the like.

In the above general formula (I), D is a diisocyanate residue [when b is 1 in general formula (I)] or a triisocyanate residue [when b is 2 in general formula (I)]. .
The type of the diisocyanate compound and triisocyanate compound from which the residue D is derived is not particularly limited, and may be any of aliphatic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, and aromatic triisocyanate.
Specific examples of the residue D include isophorone diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3′-dichloro-4,4′-phenylmethane diisocyanate, Name residues obtained by removing two isocyanate groups from diisocyanate compounds such as toluylene diisocyanate, triphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylene diisocyanate Can do.
Residue D is a trimer of a diisocyanate compound and is represented by the following general formula (α-i);

（式中、Ｒ⁴、Ｒ⁵、Ｒ⁶は脂肪族または芳香族の２価の炭化水素基を示す。）
で表されるイソシアヌレート体（イソシアヌレート環を有するトリイソシアネート化合物）に由来する、下記の一般式（α）；

(Wherein R ⁴ , R ⁵ and R ⁶ represent an aliphatic or aromatic divalent hydrocarbon group.)
The following general formula (α) derived from an isocyanurate body represented by (a triisocyanate compound having an isocyanurate ring);

（式中、Ｒ⁴、Ｒ⁵、Ｒ⁶は前記と同じ基を示す。）
で表される基であってもよい。
ウレタン化アクリル化合物（Ｉ）における複数の残基Ｄは、同じであってもまたは異なっていてもよい。

(In the formula, R ⁴ , R ⁵ and R ⁶ are the same groups as described above.)
The group represented by these may be sufficient.
The plurality of residues D in the urethanized acrylic compound (I) may be the same or different.

Among them, as the residue D, the shrinkage when the photocurable resin composition is photocured becomes smaller, and furthermore, a photocured product excellent in heat resistance, reactivity, ease of handling, and the like can be obtained. Isophorone diisocyanate, hexamethylene diisocyanate, methylene bis (cyclohexanediyl) diisocyanate, isophorone diisocyanate trimer (isocyanurate), hexamethylene diisocyanate trimer (isocyanurate), methylene bis (cyclohexanediyl) diisocyanate trimer ( It is preferably a residue of an isocyanurate form.
Therefore, when the residue D is a group represented by the above general formula (α) having an isocyanurate ring, the groups R ⁴ , R ⁵ and R ⁶ in the general formula (α) are hexamethylene groups. Or (when residue D is a group derived from hexamethylene diisocyanate trimer) or methylenebiscyclohexyl group [residue D is a group derived from methylenebis (cyclohexanediyl) diisocyanate trimer In some cases, it is preferably a group represented by the following formula (β) (when the residue D is a group derived from a trimer of isophorone diisocyanate). In the group represented by the following formula (β), the bond on the left side (bond bonded directly to the cyclohexane ring) and the bond on the right side (bond bonded to the cyclohexane ring via the methylene group) Of these, the bond on the left side may be bonded to the nitrogen atom forming the isocyanurate ring, or the bond on the right side may be bonded to the nitrogen atom forming the isocyanurate ring. It may be.

In the above general formula (I), E is a direct bond (-) or a divalent aliphatic hydrocarbon group.
Specific examples when E is a divalent aliphatic hydrocarbon group include alkylene groups having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexamethylene group. be able to. When E is an alkylene group having 3 to 6 carbon atoms, it may be a linear alkylene group or a branched alkylene group.
Among them, E is a direct bond, a methylene group, an ethylene group, a linear or branched propylene group, ease of production of the urethanized acrylic compound (I), reactivity, hardness of the cured film, etc. From the point of view, it is preferable.

In the above general formula (I), a is 1, 2 or 3, and b is 1 or 2.
In the above general formula (I), d is 0, 1, 2, 3 or 4, e is 0, 1, 2, 3 or 4, f is 0, 1, 2, 3 or 4, The sum of d and e is 2, 3 or 4, and the sum of d and f is an integer of 1 or more.
The urethanized acrylic compound (I) has a formula “—E—C (R ³ ) _{3 -a—} CH ₂ —O—CO—C (R ¹ ) ═CH ₂ ” (formula Wherein R ¹ , R ³ , E and a are the same as those described above), and one or more formulas “—O bonded to the residue A in a portion close to the center of the molecule. A group represented by —CH ₂ —CH (—) — CH ₂ —O—CO—C (R ² ) ═CH ₂ ”(wherein R ² is as defined above) and / or the formula“ —O—CH ₂ —CH (OH) —CH ₂ —O—CO—C (R ² ) ═CH ₂ ”(wherein R ² is the same as above), and is polymerizable (crosslinkable). (Meth) acryloyloxy groups are distributed throughout the urethanized acrylic compound (I) molecule.
Therefore, when the photocurable resin composition of the present invention containing the urethanized acrylic compound (I) is photocured, a crosslinked structure (polymerized structure) in which the crosslinking points are uniformly or almost uniformly distributed throughout the cured product is formed. Therefore, it is possible to form a photocured product (photocured film, molded product, three-dimensional modeled product, etc.) having a small shrinkage at the time of photocuring and excellent in dimensional accuracy, and the photocured product obtained thereby is localized. There are no defects and the uniformity of the physical properties of the entire photocured product is excellent, along with this, it has a high heat distortion temperature, excellent heat resistance, high hardness, excellent scratch resistance, and mechanical properties. Is also excellent.

In the urethanized acrylic compound (I) represented by the above general formula (I), a is 1, 2, 3, b is 1 or 2, d is 1, 2, 3, e is 0, 1, 2 or 3, f is 0, 1, 2 or 3, the sum of d and e is 2, 3 or 4, and the sum of d and f is 1, 2, 3 or 4. ) Availability of raw material compounds for producing, ease of synthesis of urethanized acrylic compound (I), viscosity of photocurable resin composition containing urethanized acrylic compound (I), hardness of cured film, It is preferable from the viewpoints of heat resistance and mechanical properties.
Although it is not limited, as a typical example of the urethanized acrylic compound (I), urethanized acrylic compounds represented by the following formulas << 1 >> to << 24 >> can be given.
In the following formula, A, E, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and a are the same as above, and R ⁷ is a diisocyanate residue.

In the urethanized acrylic compounds represented by the above formulas << 1 >> to << 12 >>, are the groups R ⁴ , R ⁵ and R ⁶ bonded to the nitrogen atom forming the isocyanurate ring a hexamethylene group (hexa A triisocyanate residue composed of a trimer of methylene diisocyanate), a methylene biscyclohexyl group or a triisocyanate group composed of a trimer of methylene bis (cyclohexanediyl) diisocyanate, the above formula (β ) (In the case of a triisocyanate group composed of a trimer of isophorone diisocyanate). When the groups R ⁴ , R ⁵ and R ⁶ are groups represented by the above formula (β), as described above, the bond on the left side (bond directly bonded to the cyclohexane ring) and the Of the right-hand bonds (bonds bonded to the cyclohexane ring via the methylene group), the left-hand bond may be bonded to the nitrogen atom forming the isocyanurate ring, or toward it. The right hand may be bonded to the nitrogen atom forming the isocyanurate ring.

In the above formula "13" ~ urethane acrylate compounds represented by the "24", preferred examples of the diisocyanate residues R ^7, isophorone diisocyanate residue, hexamethylene diisocyanate residue, methylene bis (cyclohexane-diyl) diisocyanate residues And so on.

  As a manufacturing method of a urethanized acrylic compound, the following general formula (ia);

（式中、Ｒ¹は水素原子またはメチル基、Ｒ³は水素原子または炭素数１〜４のアルキル基、Ｅは直接結合または２価の脂肪族炭化水素基を示し、ａは１、２または３である。］
で表される水酸基含有（メタ）アクリレート化合物(ｉ−ａ)と、下記の一般式(ｉ−ｂ)；

Wherein R ¹ is a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, E is a direct bond or a divalent aliphatic hydrocarbon group, and a is 1, 2 or 3.]
A hydroxyl group-containing (meth) acrylate compound (ia) represented by the following general formula (ib);

（式中、Ｄはジイソシアネート残基またはトリイソシアネート残基を示し、ｂは１または２である。）
で表されるポリイソシアネート化合物（ｉ−ｂ）を反応させて、下記の一般式(ｉ−ｃ)；

(In the formula, D represents a diisocyanate residue or a triisocyanate residue, and b is 1 or 2.)
And a polyisocyanate compound (ib) represented by the following general formula (ic):

（式中、Ｒ¹は水素原子またはメチル基、Ｒ³は水素原子または炭素数１〜４のアルキル基、Ｄはジイソシアネート残基またはトリイソシアネート残基、Ｅは直接結合または２価の脂肪族炭化水素基を示し、ａは１、２または２、ｂは１または２である。）
で表されるイソシアネート基含有ウレタン化アクリル化合物（ｉ−ｃ）をつくり、当該イソシアネート基含有ウレタン化アクリル化合物（ｉ−ｃ）を、１個以上のグリシジルエーテル基を有し、水酸基を有するかまたは水酸基を持たないグリシジルエーテル型エポキシ化合物にアクリル酸およびメタクリル酸の一方または両方を反応させて得られた下記の一般式（ｉ−ｄ）；

(Wherein R ¹ is a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, D is a diisocyanate residue or triisocyanate residue, E is a direct bond or divalent aliphatic carbonization) Represents a hydrogen group, a is 1, 2 or 2, and b is 1 or 2.)
Or an isocyanate group-containing urethanized acrylic compound (ic) represented by the formula: wherein the isocyanate group-containing urethanized acrylic compound (ic) has one or more glycidyl ether groups and a hydroxyl group or The following general formula (id) obtained by reacting one or both of acrylic acid and methacrylic acid with a glycidyl ether type epoxy compound having no hydroxyl group;

［式中、Ｒ²は水素原子またはメチル基、Ａは１個以上のグリシジルエーテル基を有し、水酸基を有するかまたは有しないグリシジルエーテル型エポキシ化合物にアクリル酸および／またはメタクリル酸を反応させて得られたエポキシ（メタ）アクリレート体からグリシジル基と（メタ）アクリル酸との反応により生成した構造部分および水酸基部分を除いた残基を示し、ｅは０、１、２、３または４、ｇは１〜８の整数である。］
で表されるエポキシ（メタ）アクリレート（ｉ−ｄ）と反応させて、下記の一般式(Ｉ)；

[Wherein R ² represents a hydrogen atom or a methyl group, A represents one or more glycidyl ether groups, and a glycidyl ether type epoxy compound having or not having a hydroxyl group is reacted with acrylic acid and / or methacrylic acid. The residue obtained by removing the structural part and the hydroxyl part produced by the reaction of a glycidyl group and (meth) acrylic acid from the obtained epoxy (meth) acrylate body, e is 0, 1, 2, 3 or 4, g Is an integer of 1-8. ]
Is reacted with an epoxy (meth) acrylate (id) represented by the following general formula (I):

［式中、Ｒ¹およびＲ²はそれぞれ独立して水素原子またはメチル基、Ｒ³は水素原子または炭素数１〜４のアルキル基、Ａは１個以上のグリシジルエーテル基を有し、水酸基を有するかまたは有しないグリシジルエーテル型エポキシ化合物にアクリル酸およびメタクリル酸の一方または両方を反応させて得られたエポキシ（メタ）アクリレート体から、グリシジル基と（メタ）アクリル酸との反応により生成した構造部分およびイソシアネート基と反応した水酸基部分を除いた残基、Ｄはジイソシアネート残基またはトリイソシアネート残基、Ｅは直接結合または２価の脂肪族炭化水素基を示し、ａは１、２または３、ｂは１または２、ｄは０、１、２、３または４、ｅは０、１、２、３または４、ｆは０、１、２、３または４であって且つｄとｅの合計が２、３または４であり、ｄとｆの合計が１以上の整数である。］
で表されるウレタン化アクリル化合物（Ｉ）を製造する本発明の製造方法が好ましく採用される。

Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A has one or more glycidyl ether groups, Structure formed by reaction of glycidyl group and (meth) acrylic acid from epoxy (meth) acrylate body obtained by reacting one or both of acrylic acid and methacrylic acid with or without glycidyl ether type epoxy compound A moiety and a residue excluding the hydroxyl group reacted with an isocyanate group, D is a diisocyanate residue or a triisocyanate residue, E is a direct bond or a divalent aliphatic hydrocarbon group, a is 1, 2 or 3, b is 1 or 2, d is 0, 1, 2, 3 or 4, e is 0, 1, 2, 3 or 4, f is 0, 1, 2, 3 or 4 and The sum of e is 2, 3 or 4, the sum of d and f is an integer of 1 or more. ]
The production method of the present invention for producing a urethanized acrylic compound (I) represented by

  Specific examples of the hydroxyl group-containing (meth) acrylate compound (ia) represented by the general formula (ia) include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, and octane. Mono (meth) acrylates of aliphatic diols having 1 to 8 carbon atoms such as diols, di (meth) acrylates of aliphatic triols such as glycerin and trimethylolpropane, tri (meth) acrylates of pentaerythritol And poly (meth) acrylic acid esters of dipentaerythritol, and one or more of these can be used.

Specific examples of the polyisocyanate compound (ib) represented by the general formula (ib) include isophorone diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and phenylene. Diisocyanate, 3,3′-dichloro-4,4′-phenylmethane diisocyanate, toluylene diisocyanate, triphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylene diisocyanate Diisocyanate compounds such as triisocyanate compounds composed of trimerized isocyanurates of these diisocyanate compounds. Can be mentioned.
Among them, as the polyisocyanate compound (ib), the photocuring resin composition has a smaller shrinkage when photocured, and is excellent in heat resistance, ease of handling, hardness of a cured film, and the like. From the viewpoint of obtaining a product, isophorone diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate trimer (isocyanurate), and hexamethylene diisocyanate trimer (isocyanurate) are preferably used.

  In the production of the isocyanate group-containing urethanized acrylic compound (ic) represented by the general formula (ic), when the polyisocyanate compound (ib) is a diisocyanate compound, 1 mol of the diisocyanate compound. 1 mol or almost 1 mol of the (meth) acrylate compound (ia) having a hydroxyl group, particularly a diisocyanate compound: the (meth) acrylate compound (ia) having a hydroxyl group = 1: 0.9-1. It is preferably used at a molar ratio of 2. Further, when the polyisocyanate compound (ib) is a triisocyanate group compound, 2 moles or almost 2 moles of (meth) acrylate compound (ia) having a hydroxyl group with respect to 1 mole of the triisocyanate compound, particularly Triisocyanate compound: (meth) acrylate compound having hydroxyl group (ia) = 1: It is preferably used in a molar ratio of 1.8 to 2.4.

The reaction between the hydroxyl group-containing (meth) acrylate compound (ia) and the polyisocyanate compound (ib) is, for example, dibutyltin dilaurate, lead naphthenate, potassium acetate, organic titanium, organic zirconium, triethylenediamine, diazabicyclo. It is preferable to use a urethanization catalyst such as undecene, tetraalkylenediamine, and triethylphosphine from the viewpoint of promoting the urethanization reaction. In this case, a polymerization inhibitor of (meth) acrylate group (for example, methyl) Hydroquinone, hydroquinone, etc.) may be further used.
In the reaction of the hydroxyl group-containing (meth) acrylate compound (ia) and the polyisocyanate compound (ib), a temperature of 50 to 150 ° C., particularly 70 to 120 ° C. is preferably employed.

The epoxy (meth) acrylate (id) represented by the above general formula (id) has one or more glycidyl ether groups and has a hydroxyl group or no hydroxyl group. Is a compound obtained by allowing one or both of acrylic acid and methacrylic acid to react with each other to convert a glycidyl group (epoxy group) in the glycidyl ether type epoxy compound into a (meth) acrylic acid ester group.
In the production of the epoxy (meth) acrylate (id), it is preferable to esterify all of the glycidyl groups in the glycidyl ether type epoxy compound with acrylic acid and / or methacrylic acid. Acrylic acid and / or methacrylic acid are reacted at a ratio of one (1 mol) or almost one (1 mol) to one epoxy group (glycidyl group) (1 equivalent) in the ether type epoxy compound. Is preferred.

  Specific examples of the epoxy (meth) acrylate (id) include those having 1 to 10 carbon atoms such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol. An epoxy (meth) acrylate obtained by reacting a glycidyl group of a monoglycidyl ether of an aliphatic diol with a (meth) acrylic acid; each of the two glycidyl groups of the diglycidyl ether of an aliphatic diol having 1 to 10 carbon atoms described above ( Epoxy (meth) acrylate reacted with (meth) acrylic acid; C1-C1 such as glycerin, butanetriol, pentanetriol, hexanetriol, trimethylolpropane, heptanetriol, octanetriol, decanediol Epoxy (meth) acrylate in which (meth) acrylic acid was reacted with glycidyl group of monoglycidyl ether of aliphatic triol; (meth) acrylic acid was reacted with two glycidyl groups of diglycidyl ether of aliphatic triol described above Epoxy (meth) acrylate; Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with three glycidyl groups of the triglycidyl ether of aliphatic triol described above; Glycidyl of monoglycidyl ether of aliphatic tetraol such as pentaerythritol Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with the group; Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with two glycidyl groups of the diglycidyl ether of the aliphatic tetraol described above; Fat described above Trio An epoxy (meth) acrylate in which (meth) acrylic acid is reacted with three glycidyl groups of triglycidyl ether of (4); (meth) acrylic acid is present on four glycidyl groups of tetraglycidyl ether of an aliphatic tetraol such as pentaerythritol Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with the glycidyl group of monoglycidyl ether of aliphatic pentaol such as reacted epoxy (meth) acrylate; two glycidyl of diglycidyl ether of aliphatic pentaol described above Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with a group; Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with three glycidyl groups of the triglycidyl ether of the aliphatic pentaol described above; Tetra of the group pentaol Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with four glycidyl groups of glycidyl ether; Epoxy in which (meth) acrylic acid is reacted with five glycidyl groups of pentaglycidyl ether of aliphatic pentaol described above (Meth) acrylate; epoxy (meth) acrylate in which glycidyl group of monoglycidyl ether of aliphatic hexaol such as dipentaerythritol is reacted with (meth) acrylic acid; two glycidyl of diglycidyl ether of aliphatic hexaol described above Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with the group; epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with three glycidyl groups of the triglycidyl ether of the aliphatic hexaol described above; Aliphatic hexaol tet Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with four glycidyl groups of glycidyl ether; Epoxy in which (meth) acrylic acid is reacted with five glycidyl groups of pentaglycidyl ether of aliphatic hexaol described above ( Examples thereof include an epoxy (meth) acrylate selected from epoxy (meth) acrylates in which (meth) acrylic acid is reacted with six glycidyl groups of the hexaglycidyl ether of the above-described aliphatic hexaol.

In the present invention, one or more of the above-described epoxy (meth) acrylates can be used as the epoxy (meth) acrylate (id) in the production of the urethanized acrylic compound (I).
Among them, in the present invention, as the epoxy (meth) acrylate (id), an epoxy (meth) acrylate in which (meth) acrylic acid has reacted with all three glycidyl groups of the triglycidyl ether of trimethylolpropane, An epoxy (meth) acrylate in which (meth) acrylic acid has reacted with each of the two glycidyl groups of the diglycidyl ether of methylolpropane, and an epoxy (meth) acrylic acid in the glycidyl group of the monoglycidyl ether of trimethylolpropane ( As for (meth) acrylate and the like, the epoxy (meth) acrylate (id) is easily available, and the photo-curable resin composition containing the urethanized acrylic compound (I) has excellent dimensional accuracy, and the resistance of the cured film is improved. It is preferably used because of its good solvent properties.

In producing the epoxy (meth) acrylate (id) represented by the above general formula (id), a glycidyl ether having one or more glycidyl ether groups and having a hydroxyl group or no hydroxyl group. The reaction of the epoxy compound with one or both of acrylic acid and methacrylic acid may be carried out in the presence of an esterification catalyst such as triphenylphosphine, quaternary ammonium salt, or tertiary amine, if necessary. When the oxidization catalyst is used, the reaction between the glycidyl ether type epoxy compound and acrylic acid and / or methacrylic acid is promoted.
Moreover, it is preferable to perform the production reaction of epoxy (meth) acrylate (id) in the presence of a polymerization inhibitor (for example, methylidroquinone, hydroquinone, etc.).
In addition, it is preferable that the production reaction of the epoxy (meth) acrylate (id) is performed while air is blown into the reaction solution because generation of a polymer component can be suppressed.

In producing the urethanized acrylic compound (I) by reacting the epoxy (meth) acrylate (id) with the isocyanate group-containing urethanized acrylic compound (ic), the epoxy (meth) acrylate (id) is used. By changing / adjusting the amount of the isocyanate group-containing urethanized acrylic compound (ic) relative to the amount of hydroxyl groups (isocyanate-reactive hydroxyl groups), d, e and f in the above general formula (I) Various urethane-modified acrylic compounds (I) having different numerical values can be obtained.
In general, the molar ratio (equivalent ratio) of [total of isocyanate-reactive hydroxyl groups possessed by epoxy (meth) acrylate (id)]: [isocyanate groups in isocyanate group-containing urethanized acrylic compound (ic)]. ) Is preferably 1: 0.1 to 1, more preferably 1: 0.1 to 1, still more preferably 1: 0.1 to 0.3.
If the proportion of the isocyanate group-containing urethanized acrylic compound (ic) is too large out of the above range, unreacted isocyanate groups remain, the stability of the urethanized acrylic compound (I) is lowered, and the cured product becomes cloudy. Etc. occur. On the other hand, if the proportion of the isocyanate group-containing urethanized acrylic compound (ic) is too small, the strength of the cured product tends to be insufficient.

The reaction of the isocyanate group-containing urethanized acrylic compound (ic) and the epoxy (meth) acrylate (id) may be performed without using a solvent, but a non-reactive organic solvent (for example, butyl acetate, It is preferable to carry out in ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. from the viewpoints of smooth progress of the reaction, coating properties, and the like. The amount of the organic solvent used in that case is preferably 5 to 95 parts by mass with respect to 100 parts by mass in total of the isocyanate group-containing urethanized acrylic compound (ic) and the epoxy (meth) acrylate (id). 5-50 mass parts is more preferable.
The reaction of the isocyanate group-containing urethanized acrylic compound (ic) and the epoxy (meth) acrylate (id) is preferably performed in the presence of a urethanization catalyst, and the reaction temperature is generally 50 to 150 ° C., In particular, a temperature of 70 to 120 ° C. is preferably employed.

  The photocurable resin composition of the present invention may contain only one urethane-modified acrylic compound (I) included in the category of the general formula (I) as the urethane-modified acrylic compound (I), Or you may contain the 2 or more urethanized acrylic compound (I) contained in the category of said general formula (I).

The photocurable resin composition of the present invention may contain only the urethanized acrylic compound (I) as the radical polymerization compound, or together with the urethanized acrylic compound (I), other than the urethanized acrylic compound (I). Other radical polymerizable compounds (II) [hereinafter sometimes referred to as “other radical polymerizable compounds (II)”] may be contained.
When the photocurable resin composition of the present invention contains another radical polymerizable compound (II) together with the urethanized acrylic compound (I), when the other radical polymerizable compound (II) is irradiated with light A radically polymerizable compound having a carbon-carbon unsaturated bond that can react with the urethanized acrylic compound (I) and / or the radically polymerizable compound (II) can react with each other to form a cured product. Any of them can be used, and among them, (meth) acrylic compounds and / or allylic compounds are preferably used.
The other radical polymerizable compound (II) may be a monofunctional compound alone, a polyfunctional compound alone, or a monofunctional compound and a polyfunctional compound in combination.
Further, the other radical polymerizable compound (II) may be a low molecular weight monomer, oligomer, or a compound having a certain degree of molecular weight.
The photocurable resin composition of the present invention may contain only one kind of radically polymerizable compound as another radically polymerizable compound (II), or contains two or more kinds of radically polymerizable compounds. You may do it.

  Specific examples of other radical polymerizable compound (II) that can be used in the photocurable resin composition of the present invention include, but are not limited to, ethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, butane Diol (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate, (poly) propylene glycol mono Monofunctional radical polymerization of mono (meth) acrylates such as (meth) acrylate and t-butyl (meth) acrylate, (meth) acrylamides such as morpholine (meth) acrylamide, N-vinylcaprolactone and styrene Products; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di ( (Meth) acrylate, 1,6-hexane diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, ethoxylated modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate 2 or more of relate, propoxylated modified trimethylolpropane tri (meth) acrylate, dicyclopentenyl di (meth) acrylate, diallyl phthalate, diallyl fumarate, ethoxylated modified bisphenol A diacrylate, propoxylated modified bisphenol A diacrylate, etc. A polyfunctional radically polymerizable compound having an unsaturated group of: urethane-modified acrylic compound other than urethane-modified acrylic compound (I), epoxy (meth) acrylate, ester (meth) acrylate other than epoxy (meth) acrylate, and the like. it can.

In the photocurable resin composition of the present invention, one or more of the above-mentioned radical polymerizable compounds can be used as the other radical polymerizable compound (II).
When the photocurable resin composition of the present invention contains another radical polymerizable compound (II) together with the urethanized acrylic compound (I), as the other radical polymerizable compound (II), monophorin (meth) acrylamide and When dicyclopentenyl di (meth) acrylate is cured with light, the volume shrinkage is smaller and the dimensional stability becomes better, and the cured product obtained by photocuring has the heat resistance and mechanical properties. It is preferably used because it becomes better.

When the photocurable resin composition of the present invention contains other radical polymerizable compound (II) together with urethanized acrylic compound (I), urethanized acrylic compound (I) and other radical polymerizable compound (II) Is preferably contained in a mass ratio of urethane-modified acrylic compound (I): other radical polymerizable compound (II) = 90: 10 to 10:90, and contained in a weight ratio of 80:20 to 20:80. It is more preferable.
By containing the urethanized acrylic compound (I) and the other radical polymerizable compound (II) in the above weight ratio, the cured product obtained by photocuring has excellent heat resistance, hardness, mechanical properties, etc. It becomes.
When the content ratio of the urethanized acrylic compound (I) is less than the above range [when the content ratio of the other radical polymerizable compound (II) is more than the above range], the heat resistance of the cured product obtained by photocuring Properties, hardness, mechanical properties, etc. are likely to deteriorate, and the shrinkage of the cured product may increase.

  Moreover, the photocurable resin composition of this invention may contain only a urethanized acrylic compound (I) as a photopolymerizable compound, or a urethanized acrylic compound (I) and other radically polymerizable compounds ( II) alone, or together with the urethanized acrylic compound (I) or with the urethanized acrylic compound (I) and other radical polymerizable compounds (II), epoxy compounds, oxetane compounds, other cations One type or two or more types of polymerizable compounds may be contained.

The photocurable resin composition of the present invention contains a photoradical polymerization initiator together with the urethanized acrylic compound (I) or together with the urethanized acrylic compound (I) and the other radical polymerizable compound (II).
As the photopolymerization initiator (III), any photoradical polymerization initiator conventionally used in photocurable resin compositions containing a radical polymerizable compound can be used and is not particularly limited.
Although not specified, specific examples of the radical photopolymerization initiator that can be used in the photocurable resin composition of the present invention include 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, acetophenone, 3- Methyl acetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-propiophenone, 2-hydroxy-2-methyl-propiophenone, p-dimethylaminoacetophenone, p-t-butyldichloroacetophenone, p-t-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenylketono, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzopheno , Xanthone, fluorenone, benzaldehyde, it may be mentioned anthraquinone, triphenylamine, carbazole and the like, may be used alone or two or more of these.
The use amount of the photo radical polymerization initiator is preferably 0.1 to 10% by mass, and 1 to 5% by mass based on the total mass of the radical polymerizable compound contained in the photocurable resin composition. It is more preferable.

  When the photocurable resin composition of the present invention further contains a cation polymerizable compound together with the urethanized acrylic compound (I) or together with the urethanized acrylic compound (I) and other radical polymerizable compound (II). Further, a photocationic polymerization initiator is further contained. As the photocationic polymerization initiator at that time, any of the photocationic polymerization initiators conventionally used in photocurable resin compositions containing a cationically polymerizable compound can be used.

The photocurable resin composition of the present invention may be a non-solvent type photocurable resin composition containing no solvent, or a solvent type photocurable resin composition containing an organic solvent. Good.
When the photocurable resin composition of the present invention is a solvent-type photocurable resin composition, it should be an organic solvent that does not impair the photocuring characteristics of the photocurable resin composition, the physical properties of the resulting photocured product, and the like. Examples of organic solvents that can be used in the photocurable resin composition of the present invention include alcohols such as ethanol, propanol, isopropanol and butanol, aromatic hydrocarbons such as toluene and xylene, and ethyl acetate. And acetates such as butyl acetate, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and one or more of these can be used.
When the organic solvent is used, the amount used is preferably 0.1 to 90% by mass, and 30 to 70% by mass, based on the total mass of the polymerizable compounds contained in the photocurable resin composition. It is more preferable.

The photocurable resin composition of the present invention can contain other components as necessary in addition to the above-described components. Examples of the other components include leveling agents, surfactants, and organic polymers. A modifier, an organic plasticizer, an organic or inorganic solid fine particle, etc. can be mentioned, These 11 types or 2 types or more can be contained as needed.
Examples of the organic solid fine particles include cross-linked polystyrene fine particles, cross-linked polymethacrylate fine particles, polyethylene fine particles, and polypropion fine particles. Examples of inorganic solid fine particles include glass beads and talc fine particles. And silicon oxide fine particles.
When organic solid fine particles and / or inorganic solid fine particles are contained in the photocurable resin composition of the present invention, the photocurable resin composition is photocured when treated with a silane coupling agent such as aminosilane, epoxysilane, or acrylicsilane. It is often preferable that the mechanical strength of the cured product obtained is improved. In the case of containing polyethylene solid fine particles and / or polypropylene solid fine particles treated with a silane coupling agent, polyethylene solid fine particles and / or polypropylene obtained by copolymerizing about 1 to 10% by mass of an acrylic acid compound. It is preferable to use solid fine particles because the affinity with the silane coupling agent is increased.

The viscosity of the photocurable resin composition of the present invention can be adjusted according to the application and use mode. Generally, when measured using a rotary B-type viscometer, the viscosity is 100 to 100 at room temperature (25 ° C.). A viscosity of about 500,000 mPa · s is preferable from the viewpoint of handleability, film-forming property, moldability, three-dimensional formability, and the like, and more preferably about 300 to 400,000 mPa · s.
For example, when the photocurable resin composition of the present invention is used for optical three-dimensional modeling, a three-dimensional model is optically produced when the viscosity at the normal temperature (25 ° C.) is in the range of 300 to 10,000 mPa · s. The handling property at the time becomes good, and the target three-dimensional object can be manufactured smoothly with high dimensional accuracy.
Moreover, when using the photocurable resin composition of this invention for manufacture of a photocurable film, when the viscosity in the above-mentioned normal temperature (25 degreeC) shall be the range of 10-100,000 mPa * s, when forming a photocurable film. Good coatability, smoothness, handling, etc.
The viscosity of the photocurable resin composition is determined by selecting the type of urethane-modified acrylic compound (I) and other radical polymerizable compound (II), adjusting the blending ratio of the two, whether or not an organic solvent is used, and the amount used. It can be adjusted by adjusting.

  The photo-curable resin composition of the present invention can be stored in a state where light can be blocked, so that a good light can be obtained while preventing denaturation and polymerization at a temperature of 10 to 40 ° C. for a period of about 6 to 18 months. It can be stored stably while maintaining the curing performance.

The photo-curable resin composition of the present invention is effectively used in various applications such as the production of a three-dimensional object by optical three-dimensional modeling, the production of a molded body, the formation of a cured film (coating material) such as a hard coat, and a photoresist. can do.
When an optical three-dimensional model or a three-dimensional model is manufactured using the photocurable resin composition of the present invention, the shrinkage at the time of photocuring is small, the dimensional accuracy is excellent, and the heat distortion temperature is high and the heat resistance is high. In addition, it is possible to smoothly produce a three-dimensionally shaped product and a molded body having excellent workability, excellent hardness, and excellent mechanical properties.

In addition, when the photocurable resin composition of the present invention is used for forming a cured film (coating material), it has a small shrinkage during photocuring and is excellent in heat resistance, hardness, mechanical properties, and scratch resistance. A cured film can be formed on various substrates. Examples of the substrate at that time include films, sheets, and molded articles made of various plastics such as polymethyl methacrylate, polycarbonate, polystyrene, polyethylene terephthalate, triacetyl cellulose, and cycloolefin polymers.
For forming a cured film on the surface of various plastic films, sheets, molded articles, etc., using the photocurable resin composition of the present invention for improving scratch resistance, etc., a conventionally known photocurable resin is used. Known methods such as a roll coating method, a dip coating method, a spray coating method, and a curtain coating method, which are coating methods of the composition, can be applied.
The thickness of the cured film to be formed on the substrate (film thickness after curing) is improved surface hardness, warpage prevention (curling prevention) of the cured film formed by irradiating active energy rays, sufficient film strength, From the viewpoint of production cost and the like, it is preferably 0.5 to 50 μm, more preferably 1 to 30 μm, and still more preferably 1 to 20 μm.

The active energy ray irradiated when the photocurable resin composition of the present invention is cured is not limited as long as it is an energy ray having an energy amount capable of activating the photopolymerization initiator. For example, visible rays, ultraviolet rays, electrons X-ray, X-ray, radiation and the like. Among them, ultraviolet rays are preferably used from the viewpoints of handleability, economic efficiency, industrial suitability, etc., and as their radiation sources, ultraviolet lasers (semiconductor excited solid lasers, Ar lasers, He-Cd lasers, etc.), high pressure mercury lamps, ultra A high-pressure mercury lamp, mercury lamp, xenon lamp, halogen lamp, metal halide lamp, ultraviolet LED (issuing diode), fluorescent lamp, or the like can be used. The dose of ultraviolet rays is preferably from ^{10~5000mJ / cm 2, 100~2000mJ / cm} 2 is more preferable.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples.
In the following examples, measurement of viscosity of urethanized acrylic compound and photocurable resin composition, measurement of volumetric shrinkage during photocuring, evaluation of heat resistance of cured product obtained by photocuring (of thermal deformation temperature) Measurement), measurement of hardness and mechanical properties (tensile properties), measurement of hardness (pencil hardness) of a cured film obtained by photocuring, and evaluation of scratch resistance were performed as follows.

(1) Viscosity of urethanized acrylic compound and photocurable resin composition:
In accordance with JIS K7117-2, a cone-plate type viscometer (cone plate type viscometer) with a constant temperature water bath capable of controlling the temperature of the measurement sample (urethane-modified acrylic compound or photocurable resin composition) The viscosity at 25 ° C. was measured, and the average of three measurements was taken as the viscosity value.

(2) Volume shrinkage ratio during photocuring of the photocurable resin composition:
The specific gravity (d ₀ ) of the photo-curable resin composition before photo-curing and the photo-cured product obtained by photo-curing the ultraviolet ray (high pressure mercury lamp) (wavelength 365 nm; intensity 3.0 mW / cm ² ) for 20 minutes From the specific gravity (d ₁ ) of the material that had been irradiated and post-cured (post-cured), the shrinkage rate was determined by the following formula (1).
Shrinkage rate (%) = {(d ₁ −d ₀ ) / d ₁ } × 100 (1)

(3) Heat resistance (thermal deformation temperature) of the photocured product:
The photocured material (bar-shaped test piece based on JIS K-7171) produced in the following examples was irradiated with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 3.0 mW / cm ² ) for 20 minutes for post-curing. JIS K-7207 (Method A) that applies a load of 1.81 MPa to the test piece using “HDT tester 6M-2” manufactured by Toyo Seiki Co., Ltd. and 0.45 MPa for the test piece In accordance with JIS K-7207 (A method) to which a load of 1 is applied, the thermal deformation temperature of the test piece was measured.

(4) Hardness of photocured product:
The photocured material (dumbbell-shaped test piece based on JIS K-7113) produced in the following examples was irradiated with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 3.0 mW / cm ² ) for 20 minutes for post-curing. The hardness (Shore D hardness) of the post-cured material was measured by a durometer method according to JIS K-6253 using an “Asker D-type hardness meter” manufactured by Kobunshi Keiki Co., Ltd.

(5) Mechanical properties of photocured material (tensile breaking strength, tensile breaking elongation, tensile elastic modulus):
The photocured material (dumbbell-shaped test piece based on JIS K-7113) produced in the following examples was irradiated with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 3.0 mW / cm ² ) for 20 minutes for post-curing. (Post-cure) was used, and the tensile strength at break (tensile strength), tensile elongation at break (tensile elongation) and tensile elastic modulus of the test piece were measured according to JIS K-7113.

(6) Pencil hardness of the cured film:
In accordance with JIS K5600-5-4, using a pencil with a core hardness of 2B-4H, tilting the pencil at an angle of 45 degrees, applying a load of 750 g from the top of the pencil, and at a speed of 30 mm / min, The cured film on the test piece (polyester film on which a cured film was formed, length × width = 10 cm × 15 cm) was scratched by about 10 mm (a pencil was allowed to run about 10 mm on the cured film), and the degree of damage was visually confirmed. The same test was performed 5 times using the same hardness pencil for the same cured film, and the pencil lead when the scratch was not scratched or was scratched only once out of 5 times. The hardness was defined as the pencil hardness of the cured film. The pencil hardness of the cured film is preferably F or more, more preferably H or more, and further preferably 2H or more.

(7) Damage resistance of cured film:
2 cm ² of steel wool # 0000 (“Bonster” manufactured by Nippon Steel Wool Co., Ltd.) was placed on the cured film of a test piece (polyethylene terephthalate film on which a cured film was formed, length × width = 10 cm × 15 cm). With a load of 500 g per cm ² , the cured film was reciprocated 100 times at a moving speed of 600 cm / min, and the number of scratches generated in the area of vertical × horizontal = 1 cm × 1 cm at the center of the cured film was visually observed. The scratch resistance was evaluated according to the following evaluation criteria.
[Evaluation criteria for scratch resistance of cured film]
A: The number of scratches is 10 or less.
○: The number of scratches is 11-20.
Δ: The number of scratches is 21-30.
X: The number of scratches is 31 or more.

<< Example 1 >> [Production of Urethane Acrylic Compound (I)]
(1) Trimethylolpropane polyglycidyl ether ("SR-TMP" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent = 137; about 50 mol% trimethylolpropane triglycidyl ether, about 40 mol% trimethylolpropane diglycidyl ether and trimethylolpropane A mixture of about 10 mol% of methylolpropane monoglycidyl ether) 137.0 g (1 equivalent) was charged into a 500 mL four-necked flask equipped with a stirrer, temperature controller, gas inlet tube, thermometer and reflux condenser. Then, 0.627 g (0.0024 mol) of triphenylphosphine as a catalyst and 0.21 g of methylhydroquinone as a polymerization inhibitor were added, air was supplied from the gas introduction pipe below the liquid level, and oxygen in the exhaust gas from the reflux condenser was added. Blowing was performed so that the concentration was 20 to 21%. 72.0 g (1.0 mol) of acrylic acid was charged into a dropping funnel with a side tube, and the liquid in the dropping funnel was added dropwise to the four-necked flask kept at 70 to 80 ° C. with stirring for 1 hour. and, performing after completion of the dropwise addition 100 to 110 ° C. 10 hours raising the reaction temperature to the reaction, the acid value of 1.0 mgKOH / g, trimethylolpropane triglycidyl ether tri represented by the following formula (i-d _a) About 50% by mass of acrylate (i-d _a ), about 40% by mass of trimethylolpropane diglycidyl ether diacrylate (i-d _b ) represented by the following chemical formula (i-d _b ) and the following chemical formula (i- the resulting d _c) trimethylolpropane monoglycidyl ether monoacrylate represented by (consisting of i-d _c of about 10 wt% epoxy acrylate bodies (OH eq 209) the .

(2) (i) An isophorone diisocyanate trimer (manufactured by Sumika Bayer Urethane Co., Ltd., “Desmodule” Z-4370 ”, NCO equivalent 359, concentration 70% by mass) 359 g (1.0 equivalent) and 0.9 g of dibutyltin dilaurate were charged, and the mixture was heated to an internal temperature of 70 to 80 ° C. with stirring.
(Ii) A solution prepared by uniformly mixing and dissolving 0.43 g of methylhydroquinone in 428.0 g (2.0 equivalents) of 2-hydroxy-3-acryloyloxypropyl methacrylate (OH equivalent = 214) is kept at 50 ° C. in advance. The dropping funnel with a side tube was charged, and the liquid in the dropping funnel was dropped into the four-necked flask (i) above while stirring from the time when the internal temperature of the flask reached 60 ° C. The mixture was stirred for 24 hours at the same temperature while maintaining the temperature of the contents of the flask at 70 to 80 ° C. in a nitrogen atmosphere while introducing nitrogen gas into the flask, and the following chemical formula (i-c _a ) isocyanate group-containing urethane acrylate compounds represented the (i-c _a) was prepared.

［上記の化学式（ｉ−ｃ_a）中、基Ｒ⁸、Ｒ⁹およびＲ¹⁰は、上記の式（β）で表される基（イソホロンジイソシアネートから２つのイソシアネート基を除いた残基）であり、基Ｒ⁸、Ｒ⁹およびＲ¹⁰をなす当該式（β）で表される基では、向かって左側の結合手（シクロヘキサン環に直接結合した結合手）および向かって右側の結合手（メチレン基を介してシクロヘキサン環に結合した結合手）のうちのいずれか一方がイソシアヌレート環を形成している窒素原子に結合している。］

[In the above formula (i-c _a), group R ^8, R ⁹ and R ¹⁰ is a group represented by the formula (beta) (residue obtained by removing two isocyanate groups from isophorone diisocyanate) , R ⁸ , R ⁹ and R ¹⁰ , the group represented by the formula (β) includes a bond on the left side (bond directly bonded to the cyclohexane ring) and a bond on the right side (methylene group). Any one of the bonds bonded to the cyclohexane ring via is bonded to the nitrogen atom forming the isocyanurate ring. ]

(3) Then, the isocyanate group-containing urethane acrylate compound after lowering (i-c _a) above, including the temperature of the contents of the flask (2) to 60 ° C., epoxy acrylate obtained above (1) (HO equivalent 209) 209.0 g (0.33 equivalent) and 272.6 g of butyl acetate were quickly added, and the temperature of the contents of the flask was kept at 80 to 90 ° C. for 4 hours to react with the urethanized acrylic compound ( The urethaned acrylic compound (IA) represented by the following formula (IA) and the urethaned acrylic compound (I-) represented by the following formula (IB), which are included in the category of I) B) and the urethaned acrylic compound (IC) represented by the following formula (IC) are converted into a urethaned acrylic compound (IA): a urethaned acrylic compound (IB): a urethaned acrylic compound. ( IC) = A reaction product (solid content: 70% by mass) contained at a mass ratio of about 50:40:10 was obtained.

上記の式中（Ｉ−Ａ）、（Ｉ−Ｂ）および（Ｉ−Ｃ）中、Ｘは下記の式で表される基である。

In the above formulas, in (IA), (IB) and (IC), X is a group represented by the following formula.

［式中、基Ｒ⁸、Ｒ⁹およびＲ¹⁰は、上記の化学式（ｉ−ｃ_a）におけるのと同じで基である。］

Wherein the groups R ⁸ , R ⁹ and R ¹⁰ are the same as in the above chemical formula (i-c _a ). ]

(4) The reaction product obtained in (3) above is heated to 80 ° C. to remove butyl acetate (solvent), and the urethanized acrylic compounds (IA), (IB) and (I) A viscous liquid consisting of -C) was obtained.

Example 2 [Production of Composition Containing Urethane Acrylic Compound (I) and Other Radical Polymerizable Compound]
(1) Follow the same steps as (1) of Example 1, an acid value of 1.0 mgKOH / g, trimethylolpropane triglycidyl ether triacrylate represented by the above formula (i-d _a) (i- d _a ) about 50% by mass, about 40% by mass of trimethylolpropane diglycidyl ether diacrylate (i-d _b ) represented by the above chemical formula (i-d _b ) and the above chemical formula (i-d _c ) to obtain a trimethylolpropane monoglycidyl ether monoacrylate represented (i-d _c) epoxy acrylates body consisting of about 10 wt% (OH eq 209).

(2) (i) An isophorone diisocyanate trimer (manufactured by Sumika Bayer Urethane Co., Ltd., “Desmodule” Z-4370 ", NCO equivalent 359, concentration 70 mass%) 359 g (1.0 equivalent) and 1.5 g of dibutyltin dilaurate were charged, and the mixture was heated to an internal temperature of 70 to 80 ° C while stirring.
(Ii) Pentaerythritol polyacrylate (mixture comprising 57% by mass of pentaerythritol triacrylate and 43% by mass of pentaerythritol tetraacrylate: OH equivalent = 523) 1046.0 g (2.0 equivalents) uniformly with 1.0 g of methylhydroquinone The mixed and dissolved liquid is charged into a dropping funnel with a side tube that has been kept at 50 ° C. in advance, and the liquid in the dropping funnel is placed in the four-necked flask of (i) above. Was added dropwise with stirring from the time when the temperature reached 60 ° C., and the mixture was stirred at the same temperature for 2 hours while maintaining the temperature of the contents of the flask at 70 to 80 ° C. in a nitrogen atmosphere while introducing nitrogen gas into the flask. to, the following chemical formula (i-c _b) an isocyanate group-containing urethane acrylate compounds represented by the (i-c _b) Pentaerisu To give a mixture of tall tetraacrylate.

［上記の化学式（ｉ−ｃ_b）中、基Ｒ¹¹、Ｒ¹²およびＲ¹³は、上記の式（β）で表される基（イソホロンジイソシアネートから２つのイソシアネート基を除いた残基）であり、基Ｒ¹¹、Ｒ¹²およびＲ¹³をなす当該式（β）で表される基では、向かって左側の結合手（シクロヘキサン環に直接結合した結合手）および向かって右側の結合手（メチレン基を介してシクロヘキサン環に結合した結合手）のうちのいずれか一方がイソシアヌレート環を形成している窒素原子に結合している。］

[In the above chemical formula (i-c _b ), the groups R ¹¹ , R ¹² and R ¹³ are groups represented by the above formula (β) (residues obtained by removing two isocyanate groups from isophorone diisocyanate). , R ¹¹ , R ¹² and R ¹³ , the group represented by the formula (β) has a bond on the left side (bond directly bonded to the cyclohexane ring) and a bond on the right side (methylene group). Any one of the bonds bonded to the cyclohexane ring via is bonded to the nitrogen atom forming the isocyanurate ring. ]

(3) Next, the temperature of the content of the flask in the above (2) containing the isocyanate group-containing urethanized acrylic compound (i-c _b ) is lowered to 60 ° C., and then the epoxy acrylate obtained in (1) above (HO equivalent 209) 209.0 g (0.33 equivalent) and 537.4 g of butyl acetate were quickly added, and the temperature of the contents of the flask was kept at 80 to 90 ° C. to react for 4 hours. The urethanized acrylic compound (ID) represented by the following formula (ID) and the urethanized acrylic compound (I-E) represented by the following formula (IE), which are included in the category of I) E) and urethanized acrylic compound (IF) represented by the following formula (IF), urethanized acrylic compound (ID): urethanized acrylic compound (IE): urethanized acrylic compound ( IF) = about 50:40:10, and a reaction product (solid content: 70% by mass) containing pentaerythritol tetraacrylate was obtained.

上記の式中（Ｉ−Ｄ）、（Ｉ−Ｅ）および（Ｉ−Ｆ）中、Ｚは下記の式で表される基である。

In the above formulas, Z is a group represented by the following formula in (ID), (IE), and (IF).

［式中、基Ｒ¹¹、Ｒ¹²およびＲ¹³は、上記の化学式（ｉ−ｃ_b）におけるのと同じで基である。］

[Wherein the groups R ¹¹ , R ¹² and R ¹³ are the same as those in the above formula (i-c _b ). ]

(4) The reaction product obtained in (3) above is heated to 80 ° C. to remove butyl acetate (solvent), and the urethanized acrylic compounds (ID), (IE) and (I) A viscous liquid consisting of -F) and pentaerythritol tetraacrylate was obtained.

Example 3
(1) 100 parts by mass of a liquid comprising urethanized acrylic compound (IA), (IB) and (IC) obtained in Example 1, methyl isobutyl ketone and Irgacure 184 (radical polymerization initiator) 5 mass parts was mixed well and the photocurable resin composition was prepared. It was 150000 mPa * s (50 degreeC) when the viscosity of this resin composition for optical shaping | molding was measured by the above-mentioned method.
(2) Using the photocurable resin composition obtained in the above (1), photocuring was performed under the condition of 160 W 70 mW / cm ² × 500 mJ / cm ² , and length × width × height = 200 mm × 100 mm. A rectangular solid photocured product having a size of 10 mm is produced, and the photocured product is irradiated with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 3.0 mW / cm ² ) for 20 minutes to be post-cured. Then, the specific gravity was measured, and the shrinkage rate was determined by the above formula (1). As a result, it was as shown in Table 1 below.
(3) Using the photocurable resin composition obtained in the above (1), photocuring is performed under the conditions of 160 W 70 mW / cm ² × 500 mJ / cm ² , and the bar shape conforms to JIS K-7171. A test piece was made and irradiated with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 3.0 mW / cm ² ) for 20 minutes and post-cured, and then “HDT Tester 6M-” manufactured by Toyo Seiki Co., Ltd. was used. 2 ”, a test was conducted in accordance with JIS K-7207 (Method A) for applying a load of 1.81 MPa to a test piece and JIS K-7207 (Method A) for applying a load of 0.45 MPa to a test piece. When the heat distortion temperature of the piece was measured, it was as shown in Table 1 below.

(4) The hardness (Shore D hardness) of the photocured product obtained after the post-curing (post-cure) obtained in the above (2), using “Asker D-type hardness meter” manufactured by Kobunshi Keiki Co., Ltd. When measured by the durometer method according to JIS K-6253, it was as shown in Table 1 below.
(5) Using the photocurable resin composition obtained in (1) above, photocuring is performed under the conditions of 160 W 70 mW / cm ² × 500 mJ / cm ² , and a dumbbell shape conforming to JIS K-7113 A test piece (photocured product) was prepared and irradiated with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 3.0 mW / cm ² ) for 20 minutes, followed by post-curing. JIS K- According to 7113, the tensile strength at break (tensile strength), tensile elongation at break (tensile elongation), and tensile modulus of the test piece were measured and as shown in Table 1 below.
(6) After coating the photocurable resin composition obtained in (1) above on a polyethylene terephthalate film having a thickness of 125 μm, the thickness is photocured under conditions of 160 W 70 mW / cm ² × 500 mJ / cm ^2. When a cured film of about 4 μm was formed and the pencil hardness of this cured film was measured by the method described above, it was as shown in Table 1 below.
(7) The scratch resistance of the cured film formed in (6) above was evaluated by the method described above, and as shown in Table 1 below.

Example 4
(1) 73 parts by mass of a liquid comprising urethanized acrylic compound (ID), (IE) and (IF) obtained in Example 2, and pentaerythritol tetraacrylate (other radical polymerizable compound) ) 27 parts by mass and 5 parts by mass of Irgacure 184 (radical polymerization initiator) were mixed well to prepare a photocurable resin composition. It was 300000 mPa * s (25 degreeC) when the viscosity of this resin composition for optical shaping | molding was measured by the above-mentioned method.
(2) Using the photocurable resin composition obtained in (1) above, in the same manner as in (2) to (7) of Example 3, the shrinkage rate during photocuring and the heat distortion temperature of the photocured product , Hardness (Shore D hardness), tensile breaking strength (tensile strength), tensile breaking elongation (tensile elongation) and tensile elastic modulus were measured, and the pencil hardness and scratch resistance of the photocured film were examined. As shown in Table 1.

  The photocurable resin composition of the present invention containing the urethanized acrylic compound (I) can form a photocured product that is liquid at room temperature and has excellent handleability, has a small shrinkage during photocuring, and is excellent in dimensional accuracy, Since it can form a photocured product with excellent heat resistance, high hardness, excellent scratch resistance, and excellent mechanical properties, etc., manufacturing optical three-dimensional modeling, manufacturing compacts, and photocuring films Useful for various applications such as forming.

Claims (7)

The following general formula (I);

Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A has one or more glycidyl ether groups, Structure formed by reaction of glycidyl group and (meth) acrylic acid from epoxy (meth) acrylate body obtained by reacting one or both of acrylic acid and methacrylic acid with or without glycidyl ether type epoxy compound A moiety and a residue excluding the hydroxyl group reacted with an isocyanate group, D is a diisocyanate residue or a triisocyanate residue, E is a direct bond or a divalent aliphatic hydrocarbon group, a is 1, 2 or 3, b is 1 or 2, d is 0, 1, 2, 3 or 4, e is 0, 1, 2, 3 or 4, f is 0, 1, 2, 3 or 4 and The sum of e is 2, 3 or 4, the sum of d and f is an integer of 1 or more. ]
The photocurable resin composition characterized by containing the urethane-ized acrylic compound (I) represented by these, and radical photopolymerization initiator.   The photocurable resin composition according to claim 1, further comprising a radical polymerizable compound (II) other than the urethanized acrylic compound (I).   A in the above general formula (I) is an epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with a glycidyl group of an aliphatic diol monoglycidyl ether; each of two glycidyl groups of an aliphatic diol diglycidyl ether (Meth) acrylic acid reacted with (meth) acrylic acid; glycidyl group of aliphatic triol monoglycidyl ether with (meth) acrylic acid reacted with (meth) acrylic acid; aliphatic triol diglycidyl ether (Meth) acrylates in which (meth) acrylic acid is reacted with the glycidyl group of the above; epoxy (meth) acrylates in which (meth) acrylic acid is reacted with the three glycidyl groups of the aliphatic triol triglycidyl ether; All monoglycidyl ether group Epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with a sidyl group; Epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with two glycidyl groups of aliphatic tetraol diglycidyl ether; Epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with three glycidyl groups of all-triglycidyl ether; epoxy (meth) acrylic acid is reacted with four glycidyl groups of aliphatic tetraol tetraglycidyl ether ( (Meth) acrylate body; epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with glycidyl group of aliphatic pentaol monoglycidyl ether; (meth) acrylic acid on two glycidyl groups of aliphatic pentaol diglycidyl ether Reacted epoxy (meth) acrylate An epoxy (meth) acrylate in which (meth) acrylic acid is reacted with three glycidyl groups of aliphatic pentaol triglycidyl ether; (meth) acrylic is added to four glycidyl groups of aliphatic pentaol tetraglycidyl ether Epoxy (meth) acrylate body reacted with acid; epoxy (meth) acrylate body reacted with (meth) acrylic acid on 5 glycidyl groups of aliphatic pentaol pentaglycidyl ether; glycidyl group of aliphatic hexaol monoglycidyl ether (Meth) acrylate reacted with (meth) acrylic acid; epoxy (meth) acrylate reacted with (meth) acrylic acid on two glycidyl groups of aliphatic hexaol diglycidyl ether; aliphatic hexaol tri 3 glycis of glycidyl ether Epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with a zyl group; Epoxy (meth) acrylate body in which (meth) acrylic acid is reacted with four glycidyl groups of aliphatic hexaol tetraglycidyl ether; Epoxy (meth) acrylate in which (meth) acrylic acid is reacted with five glycidyl groups of all pentaglycidyl ether; Epoxy ((meth) acrylic acid is reacted with six glycidyl groups of aliphatic hexaol hexaglycidyl ether) 2. A residue obtained by removing a structural part produced by a reaction between a glycidyl group and (meth) acrylic acid and a hydroxyl part reacted with an isocyanate group from an epoxy (meth) acrylate selected from a (meth) acrylate. 2. The photocurable resin composition according to 2.   D is an isocyanurate body residue which is a trimer of a diisocyanate compound, The photocurable resin composition of any one of Claims 1-3.   5. The photocurable composition according to claim 4, wherein the isocyanurate residue is an isocyanurate residue of isophorone diisocyanate, an isocyanurate residue of hexamethylene diisocyanate, or an isocyanurate residue of methylenebis (cyclohexanediyl) diisocyanate. Resin composition. The following general formula (I)

Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A has one or more glycidyl ether groups, Structure formed by reaction of glycidyl group and (meth) acrylic acid from epoxy (meth) acrylate body obtained by reacting one or both of acrylic acid and methacrylic acid with or without glycidyl ether type epoxy compound A moiety and a residue excluding the hydroxyl group reacted with an isocyanate group, D is a diisocyanate residue or a triisocyanate residue, E is a direct bond or a divalent aliphatic hydrocarbon group, a is 1, 2 or 3, b is 1 or 2, d is 0, 1, 2, 3 or 4, e is 0, 1, 2, 3 or 4, f is 0, 1, 2, 3 or 4 and The sum of e is 2, 3 or 4, the sum of d and f is an integer of 1 or more. ]
A urethane-modified acrylic compound (I) represented by The following general formula (ia);

Wherein R ¹ is a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, E is a direct bond or a divalent aliphatic hydrocarbon group, and a is 1, 2 or 3.]
A hydroxyl group-containing (meth) acrylate compound (ia) represented by the following general formula (ib);

(In the formula, D represents a diisocyanate residue or a triisocyanate residue, and b is 1 or 2.)
And a polyisocyanate compound (ib) represented by the following general formula (ic):

(Wherein R ¹ is a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, D is a diisocyanate residue or triisocyanate residue, E is a direct bond or divalent aliphatic carbonization) Represents a hydrogen group, a is 1, 2 or 3, and b is 1 or 2.)
Or an isocyanate group-containing urethanized acrylic compound (ic) represented by the formula: wherein the isocyanate group-containing urethanized acrylic compound (ic) has one or more glycidyl ether groups and a hydroxyl group or The following general formula (id) obtained by reacting acrylic acid and / or methacrylic acid with a glycidyl ether type epoxy compound which does not have;

[Wherein R ² represents a hydrogen atom or a methyl group, A represents one or more glycidyl ether groups, and a glycidyl ether type epoxy compound having or not having a hydroxyl group is reacted with acrylic acid and / or methacrylic acid. The residue obtained by removing the structural part and the hydroxyl part produced by the reaction of a glycidyl group and (meth) acrylic acid from the obtained epoxy (meth) acrylate body, e is 0, 1, 2, 3 or 4, g Is an integer of 1-8. ]
Is reacted with an epoxy (meth) acrylate (id) represented by the following general formula (I):

Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A has one or more glycidyl ether groups, Structure formed by reaction of glycidyl group and (meth) acrylic acid from epoxy (meth) acrylate body obtained by reacting one or both of acrylic acid and methacrylic acid with or without glycidyl ether type epoxy compound A moiety and a residue excluding the hydroxyl group reacted with an isocyanate group, D is a diisocyanate residue or a triisocyanate residue, E is a direct bond or a divalent aliphatic hydrocarbon group, a is 1, 2 or 3, b is 1 or 2, d is 0, 1, 2, 3 or 4, e is 0, 1, 2, 3 or 4, f is 0, 1, 2, 3 or 4 and The sum of e is 2, 3 or 4, the sum of d and f is an integer of 1 or more. ]
A process for producing a urethanized acrylic compound (I) represented by the formula: