WO2010146801A1

WO2010146801A1 - Urethane (meth)acrylate compound and resin composition containing same

Info

Publication number: WO2010146801A1
Application number: PCT/JP2010/003830
Authority: WO
Inventors: 小木聡; 栗橋透; 小淵香津美
Original assignee: 日本化薬株式会社
Priority date: 2009-06-17
Filing date: 2010-06-09
Publication date: 2010-12-23
Also published as: TWI482791B; TW201105694A; CN102803332B; JP5757664B2; KR101664003B1; CN102803332A; JPWO2010146801A1; KR20120052192A

Abstract

Disclosed is a urethane (meth)acrylate compound (A) obtained by reacting (I) any of (i) a dipentaerythritol poly(meth)acrylate mixture (a) which comprises at least two compounds selected from a group consisting of dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate and which has a hydroxy value of 80-120 mg-KOH/g (hereinafter referred to as mixture (a)), (ii) both the mixture (a) and glycerol, and (iii) all of the mixture (a), glycerol, and a (meth)acrylate of a C_2-5 aliphatic polyol (di- to tetrol) with (II) a polyisocyanate compound (b) comprising a diisocyanate compound. Also disclosed are a resin composition comprising the urethane (meth)acrylate compound (A) and a photopolymerizataion initiator (C), a cured object formed from the resin composition, a hard coating material comprising the resin composition, and a hardcoat.

Description

Urethane (meth) acrylate compound and resin composition containing the same

The present invention includes at least two selected from the group consisting of dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. A urethane (meth) acrylate compound (A) using a dipentaerythritol poly (meth) acrylate mixture (a) having a hydroxyl value of 80 to 120 mgKOH / g as a raw material, and a resin composition containing the same, in particular, the urethane (meth) The present invention relates to a resin composition containing an acrylate compound (A) and a photopolymerization initiator, and a cured film of the resin composition. And since the cured film of the resin composition of the present invention is excellent in hardness, adhesion to a substrate, scratch resistance, etc., curl is small and cracks are less likely to occur, it can be used as a hard coat for plastic films and small casings. Useful.

Further, the cured film of the resin composition of the present invention has good adhesion to the substrate, has high hardness, and has an appropriate flexibility, so that the resin composition of the present invention is a color filter (for example, Color filters used in color liquid crystal displays, color video cameras, color digital cameras, electronic papers, etc.), black matrixes, or spacers can also be used.

Currently, lightweight, inexpensive plastics that are excellent in various properties such as processability, transparency, and optical properties are used in the industry. However, since plastics are softer than glass and have defects such as the surface being easily scratched, it is common practice to coat a hard coating agent on the plastic surface. As the hard coat agent, many thermosetting types such as silicone paints, acrylic paints, and melamine paints are known. Among these, silicone hard coat agents have been mainly used because of their excellent performance and quality. However, the silicone-based hard coat agent has a drawback that it has a long curing time and is expensive.

Therefore, a photosensitive acrylic hard coat agent has been developed and used as a hard coat agent that compensates for the disadvantages of silicone hard coat agents (see Patent Document 1). Acrylic hard coat agents are cured immediately upon irradiation with radiation such as ultraviolet rays, so that the processing speed is high, the hardness and the scratch resistance are excellent, and the cost is low. Therefore, at present, the acrylic hard coat agent has become the mainstream in the hard coat field. In particular, the acrylic hard coat agent is suitable for coating the surface of the substrate during continuous processing of a substrate film such as polyester.

Examples of the plastic base film include a polyester film, an acrylic film, a polycarbonate film, a vinyl chloride film, a triacetyl cellulose film, and a polyethersulfone film. Among them, polyester films are most widely used because of various excellent properties. This polyester film is used for applications such as glass shatterproof film, automobile light-shielding film, whiteboard surface film, system kitchen surface antifouling film, and electronic materials. CRT flat TV, touch panel, liquid crystal display (LCD) ), A functional film in plasma display (PDP), organic EL display and the like.
In addition to films, electronic device cases such as home appliance bodies and switches, mobile phones, personal computers, and MP3 players are widely used as polyester resin moldings. All of these are hard-coated to prevent the surface from being scratched. In addition to polyester, for example, a hard-coated sheet or substrate such as polycarbonate or acrylic is used for an optical disk or a liquid crystal related member around a backlight.

In recent years, a film having a hard coat layer with a function other than the performance as a hard coat called scratch resistance has been developed. For example, in the case of a display such as a CRT, LCD, or PDP provided with a film, it is difficult to see the display screen due to reflection, and the eyes are likely to get tired. Has also been done.

On the other hand, studies are also being made to improve the hardness, which is the original purpose of the hard coat. For example, Patent Document 3 attempts to improve hardness by adding polyfunctional urethane acrylate to the resin composition. However, there is a problem that the curing shrinkage of the polyfunctional urethane acrylate being used is large and cracks are observed.

In Patent Document 4, polyfunctional urethane (meth) acrylate is used in a resin composition for hard coating of an antireflection material. This hard coat is quite excellent in terms of hardness, curl resistance, scratch resistance, etc., but it is not always satisfactory and further improvements are desired.

Japanese Patent Laid-Open No. 9-48934 Japanese Patent Laid-Open No. 9-145903 JP 2001-113648 A JP 2000-187102 A

The present invention provides a cured film that is excellent in hardness and scratch resistance and has less curling and cracking, and is further superior to the above-mentioned known ones, and a urethane (meth) acrylate compound that provides the cured film and a resin composition containing the same. Is an issue.

The present inventors arrived at the present invention as a result of intensive studies to solve the above problems.

That is, the present invention relates to the following inventions.
(1) (I) (i), (ii) or (iii) below,
(I) including at least two selected from the group consisting of dipentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Dipentaerythritol poly (meth) acrylate mixture (a) (hereinafter referred to as the mixture (a)) having a hydroxyl value of 80 to 120 mgKOH / g, or
(Ii) both the mixture (a) and glycerin, or
(Iii) the mixture (a), glycerol and (meth) acrylates of C2-C5 aliphatic poly (2-4) ol,
Either
(II) a polyisocyanate compound (b) containing a diisocyanate compound,
Urethane (meth) acrylate compound (A) obtained by reacting with.
(2) The urethane (meth) acrylate compound (A) according to (1), wherein (I) is the mixture (a) of (i).
(3) The polyisocyanate compound (b) of (II) is a diisocyanate compound alone or a combination of a diisocyanate compound and a triisocyanate compound, and the ratio of the diisocyanate compound to the triisocyanate compound is 1 mol of the diisocyanate compound. The urethane (meth) acrylate compound (A) according to the above (1) or (2), wherein is a ratio of 0 to 10 mol.

(4) The urethane (meth) acrylate compound (A) according to any one of the above (1) to (3) represented by the following general formula (1):

(Wherein X is an isocyanate residue, n is an integer of 0 to 100,
Y is an organic group represented by the following general formula (2), wherein a, b and c are integers of 1 ≦ a ≦ 4, 0 ≦ b ≦ 3 and 0 ≦ c ≦ 3, respectively. And a + b + c = 4,

as well as,
A is an organic group represented by the general formula (2), wherein X is an isocyanate residue, c is 0, and a and b are integers of 1 ≦ a ≦ 5 and 0 ≦ b ≦ 4 And a + b = 5,
B is an organic group represented by the general formula (2), wherein X is an isocyanate residue, c is 0, and a and b are
(I) when B is present at the end, 1 ≦ a ≦ 5, 0 ≦ b ≦ 4, and a + b = 5,
(Ii) When B is present at a position other than the end, a and b in the formula are integers of 1 ≦ a ≦ 4, 0 ≦ b ≦ 3, and a + b = 4).

(5) (i) The polyisocyanate compound (b) is mixed with the mixture (a) and the polyisocyanate compound (b) of (II) with respect to 1 equivalent of the active hydrogen group in the mixture (a). A process for producing the urethane (meth) acrylate compound (A) according to any one of the above (1) to (4), wherein the reaction is carried out at a ratio of 0.1 to 50 equivalents of an isocyanate group in the solvent.
(6) The urethane (meth) acrylate compound (A) according to (1) or (3), wherein (I) is the mixture (a) of (ii) and glycerin.
(7) The mixture (a) and glycerin of (1) above, and the polyisocyanate compound (b) of (II) of (1) above are added to 1 equivalent of active hydrogen groups in the mixture (a). The active hydrogen group equivalent in the glycerol is 0.01 to 10 equivalents, and the isocyanate group equivalent in the polyisocyanate compound (b) (II) is 0.1 to 50 equivalents. Production method of urethane (meth) acrylate compound (A).
(8) Contains the urethane (meth) acrylate compound (A), (meth) acrylate (B) and photopolymerization initiator (C) according to any one of (1) to (4) and (6) above. Resin composition.
(9) The resin composition according to (8), which is used for hard coating.
(10) The above (1) or (3) wherein (I) is a mixture of (iii) (glycerol) and (meth) acrylate of C2 to C5 aliphatic poly (2 to 4) ol. ) Urethane (meth) acrylate compound (A).

(11) The above (1) (I) (iii), the mixture (a), glycerin and (meth) acrylates of C2-C5 aliphatic poly (2-4) ol, and (1 ) Of the polyisocyanate compound (b) of (II) with respect to 1 equivalent of active hydrogen groups in the mixture (a) and 0.01 to 10 equivalents of active hydrogen groups of glycerin and C2 to C5 aliphatic poly (2-4) The reaction is carried out at a ratio of 0.01 to 10 equivalents of active hydrogen group equivalent of (meth) acrylate of all and 0.1 to 50 equivalent of isocyanate group equivalent of polyisocyanate compound (b), (1) Or the manufacturing method of the urethane (meth) acrylate compound (A) as described in (10).
(12) The mixture (a) in (I) contains 35 dipentaerythritol penta (meth) acrylate in the area ratio (%) of high performance liquid chromatography (HPLC) with respect to the total amount of the mixture (a). The total of the three components including 90% to 100%, dipentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate added thereto is 90 to 100%, and the remaining 0 to 10% is dipentaerythritol tri (meta) The urethane (meth) acrylate compound (A) according to any one of the above (1) to (4), (6) or (10), which is a multimeric acrylate of acrylate and tripentaerythritol.
(13) The urethane (meth) acrylate compound according to any one of (1) to (4), (6), (10) or (12) above, wherein the polyisocyanate compound (b) is a diisocyanate compound alone ( A).
(14) Any of the above (1) to (3), (5), (6), (10), (12) or (13), wherein the polyisocyanate compound (b) is a combination of a diisocyanate compound and a triisocyanate compound The urethane (meth) acrylate compound (A) according to claim 1.

(15) The urethane (meth) acrylate compound (A) according to the above (13) or (14), wherein the diisocyanate compound is hexamethylene diisocyanate.
(16) The mixture (a) is a ternary mixture of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, or dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol penta (4) A mixture of acrylate and dipentaerythritol hexaacrylate, wherein the polyisocyanate compound (b) is hexamethylene diisocyanate alone or both hexamethylene diisocyanate and hexamethylene diisocyanate trimer. , (6), (10) and the urethane (meth) acrylate compound (A) according to any one of (12) to (14).
(17) The urethane (meth) acrylate compound (A) according to any one of (1) to (4), (6), (10), (12) to (16) and a photopolymerization initiator ( A resin composition containing C).
(18) The urethane (meth) acrylate compound (A) according to any one of (1) to (4), (6), (10), (12) to (16) and a photopolymerization initiator ( A cured film of a resin composition containing C).
(19) The urethane according to any one of (1) to (4), (6), (10) and (12) to (16), wherein the viscosity (60 ° C.) is 5 to 40 Pa · s. (Meth) acrylate compound (A).

By using the urethane (meth) acrylate compound (A) of the present invention, a cured film having high transparency, hardness and scratch resistance, hardly causing curling and cracking, or high transparency, suitable hardness and Provided are a resin composition that provides a cured film having flexibility and toughness, a cured product of the resin composition, a hard coat agent comprising the resin composition, and a hard coat using the same.

Hereinafter, the present invention will be described in detail.

In the present invention, at least 2 selected from the group consisting of dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate used as a raw material. Dipentaerythritol poly (meth) acrylate mixture containing seeds (a) {preferably at least two selected from the group consisting of dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate The hydroxyl value of the dipentaerythritol polyacrylate mixture (a ′)} containing is in the range of 80 to 120 mg KOH / g. When the hydroxyl value is within this range, gelation does not occur during the urethanization reaction, and the desired urethane (meth) acrylate compound (A) {preferably urethane acrylate compound (A ')} can be efficiently obtained. it can. Moreover, from the resin composition containing the obtained urethane (meth) acrylate compound (A), a hard coat having high hardness, excellent curl resistance and high flexibility can be obtained.
In addition, in this specification, when it is necessary to distinguish the said urethane (meth) acrylate compound (A) by a structure or a composition, the compound which does not contain skeleton derived from glycerol is a urethane (meth) acrylate compound (A1). ), A urethane (meth) acrylate compound (A2) containing a glycerin-derived skeleton, a compound containing a glycerin-derived skeleton and a (meth) acrylate-derived skeleton of a C2-C5 aliphatic poly (2-4) ol. It is called (meth) acrylate compound (A3).

The dipentaerythritol poly (meth) acrylate mixture (a) (hereinafter also simply referred to as poly (meth) acrylate mixture (a) or the mixture (a)) used as the raw material dehydrates dipentaerythritol and (meth) acrylic acid. It can be obtained by subjecting dipentaerythritol to (meth) acrylate by dehydration condensation reaction in the presence of a condensation catalyst such as an acid catalyst.
The mixture (a) is preferably selected from the group consisting of dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. At least three, more preferably three of dipentaerythritol tetra, penta and hexa (meth) acrylate. Usually, the mixture (a) is a mixture containing four kinds of dipentaerythritol tri, tetra, penta and hexa (meth) acrylate, or a mixture containing three kinds of dipentaerythritol tetra, penta and hexa (meth) acrylate. is there. The mixture (a) may further contain a trimeric or higher pentaerythritol acrylate such as tripentaerythritol by-produced during the condensation reaction. Of the (meth) acrylated products of dipentaerythritol, acrylated products (dipentaerythritol tri, tetra, penta, and hexaacrylate) are more preferable than methacrylated products from the viewpoint of cost.

In this invention, the content rate of each component with respect to the total amount of this mixture (a) is an area ratio (%) of a high performance liquid chromatography (HPLC), and is as follows.
Dipentaerythritol penta (meth) acrylate (preferably dipentaerythritol pentaacrylate) is 30 to 70%, preferably 30 to 60%, more preferably 35 to 55%, still more preferably 35 to 50%, A total of 85 of dipentaerythritol penta (meth) acrylate (preferably dipentaerythritol pentaacrylate) plus dipentaerythritol tetra and hexa (meth) acrylate (preferably dipentaerythritol tetra and hexaacrylate) is 85. To 100%, preferably 90 to 100%. Wherein upon dehydration condensation reaction, considering that there are by-product of said multimeric, the three parties of the total 85 to 98% Ru preferably 90 to 97% der. The remainder contains dipentaerythritol tri (meth) acrylate (preferably dipentaerythritol triacrylate) and / or a multimeric acrylate of the pentaerythritol trimer or more. In this case, the contents of dipentaerythritol tetra and hexa (meth) acrylate are about 1 to 40% (preferably about 10 to 30%) and about 15 to 40% (preferably 20 to 20%), respectively. The content of dipentaerythritol tri (meth) acrylate is about 0 to 10%, preferably 5% or less (including zero). In addition, the multimeric acrylate may be included.
The manufacturing method of the said mixture (a) is demonstrated in detail below.
As long as the said mixture (a) used as a raw material by this invention is obtained, it is not restricted to this.

Examples of the acid catalyst used in the above dehydration condensation reaction include mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid and trifluoromethanesulfonic acid, and fluorine. Examples thereof include Lewis acids such as boron ether diethyl etherate and acid ion exchange resins. These acid catalysts may be used alone or in admixture of two or more. Among these, sulfuric acid can be mentioned as a preferable acid catalyst.
The amount of the acid catalyst used is 0.01 to 50 mol%, preferably 0.1 to 20 mol%, relative to 1 mol of dipentaerythritol.

In the dehydration condensation reaction of dipentaerythritol and (meth) acrylic acid, (meth) acrylic acid is used in an amount of 0.1 to 20 mol, preferably 1 to 10 mol, per 1 mol of dipentaerythritol.

The reaction time in the dehydration condensation reaction may be in the range of 1 to 24 hours, and the reaction temperature may be in the range of 60 to 150 ° C., but is 75 to 120 ° C., more preferably 100 to 120 ° C. from the viewpoint of shortening the reaction time and preventing polymerization. Is preferred.

As a reaction solvent in the dehydration condensation reaction, an azeotropic solvent capable of distilling off water generated in the reaction is preferable. As the azeotropic solvent here, a solvent having a boiling point of 60 to 130 ° C., azeotropic with water, and easily separable from water is preferable.
Specifically, it is desirable to use a mixture of one or more non-reactive organic solvents such as benzene, toluene, n-hexane, n-heptane, and cyclohexane. Usually toluene is more preferred. The amount used is arbitrary, but is preferably 10 to 70% by mass with respect to the reaction mixture.

Usually, a commercially available (meth) acrylic acid used as a raw material is already added with a polymerization inhibitor such as 4-methoxyphenol, but a polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, Examples include phenothiazine. Moreover, cupric chloride etc. can also be used. The amount used is 0.01 to 1% by mass with respect to the reaction mixture.

The urethane (meth) acrylate compound (A) of the present invention is
(I) The following (i), (ii) or (iii),
(I) including at least two selected from the group consisting of dipentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Dipentaerythritol poly (meth) acrylate mixture (a) (hereinafter referred to as the mixture (a)) having a hydroxyl value of 80 to 120 mgKOH / g, or
(Ii) both the mixture (a) and glycerin, or
(Iii) the mixture (a), glycerol and (meth) acrylates of C2-C5 aliphatic poly (2-4) ol,
(Hereinafter also referred to as component (I)),
(II) a polyisocyanate compound (b) containing a diisocyanate compound,
It can obtain by making it react.

Any polyisocyanate compound (b) used for the production of the urethane (meth) acrylate compound (A) of the present invention can be used as long as it is a compound containing two or more isocyanate groups in one molecule. It is essential to contain a diisocyanate compound. The polyisocyanate compound (b) is preferably a diisocyanate compound alone or a combination of a diisocyanate compound and another polyisocyanate. In the case of the combined use, the combined use of a diisocyanate compound and a triisocyanate compound is particularly preferable. Examples of the polyisocyanate compound (b) that can be used in the present invention include aliphatic polyisocyanate compounds and aromatic type compounds. Examples thereof include polyisocyanate compounds, alicyclic polyisocyanates, trimer or multimer compounds thereof, burette type polyisocyanates, and allophanate type polyisocyanates. A trimer or multimeric compound means a compound in which three isocyanate groups form one or more isocyanurate ring structures.
The polyisocyanate compound (b) used in the present invention may be a diisocyanate compound alone as described above, or may be a combination of a diisocyanate compound and another polyisocyanate compound. In the case of a combined use of a diisocyanate compound and another polyisocyanate compound, preferably a combined use of a diisocyanate compound and a triisocyanate compound, any of them may be one kind or plural kinds. Usually, one type is preferable for each.

Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate (1,6-hexamethylene diisocyanate), isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and 1,3-diisocyanate cyclohexane. 1,4-diisocyanate cyclohexane, dicyclohexylmethane-4,4′-diisocyanate, 1,4-tetramethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4 -Trimethylhexamethylene diisocyanate, dimethylcyclohexane diisocyanate, 2,2,4-trimethylcyclohexane diisocyanate 2,4,4-trimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, norbornane diisocyanate, bicycloheptane triisocyanate, hexamethylene diisocyanate trimer, etc. C4-C12 aliphatic di- or triisocyanate compounds Etc.

Examples of aromatic polyisocyanate compounds include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,4-phenylene diisocyanate, 1,6-phenylene diisocyanate, and 3-tetramethyl. Examples thereof include C2 to C13 aromatic diisocyanates having 1 to 2 phenylene rings or 1 naphthalene ring, such as xylene diisocyanate and 4-tetramethylxylene diisocyanate.

Among the polyisocyanates (b), in the present invention, a diisocyanate compound alone or a combination of a diisocyanate compound and a triisocyanate compound is preferable.
The ratio of the diisocyanate compound and the other polyisocyanate compound, preferably the triisocyanate compound is such that the other polyisocyanate compound (preferably the triisocyanate compound) is 0 to 10 mol, preferably 0 to 7 mol, per 1 mol of the diisocyanate compound. More preferably, it is 0 to 5 mol, and still more preferably about 0 to 3 mol.
Of the diisocyanate compounds, aliphatic diisocyanates are preferred, and C4 to C12 aliphatic diisocyanates are more preferred. Hexamethylene diisocyanate is most preferred, and among the triisocyanate compounds, hexamethylene diisocyanate trimer is preferred.

The use ratio of the polyisocyanate compound (b) to the mixture (a) is equivalent to an isocyanate group equivalent to 1 equivalent of active hydrogen groups in the mixture (a) (the dipentaerythritol poly (meth) acrylate mixture (a)). Is usually in the range of 0.1 to 50 equivalents, preferably in the range of 0.1 to 10 equivalents. In the case of reacting glycerin, glycerin is usually in the range of 0.01 to 10 equivalents as active hydrogen group equivalent to 1 equivalent of active hydrogen group in the poly (meth) acrylate mixture (a). It is in the range of 1 to 1 equivalent.
The active hydrogen group in the mixture (a) means a hydrogen atom in the hydroxy group, and the active hydrogen groups in the (meth) acrylates of glycerin and C2 to C5 aliphatic poly (2 to 4) ol are respectively The hydrogen atom in the hydroxy group in the compound of this is meant. In the present specification, the term “hydroxyl equivalent” is also used, but it is used in the same meaning as the active hydrogen group equivalent.
The ratio of the polyisocyanate compound (b) to 1 mol of the mixture (a) is such that the hydroxyl group equivalent of the mixture (a), the isocyanate group equivalent in the polyisocyanate compound (b), glycerin and C2 to C5 fat The polyisocyanate compound (b) can be added in an amount of 0.3 mol per 1 mol of the mixture (a). It is preferable to use within the range of about ˜1 mol, preferably about 0.3 to 0.9 mol, more preferably 0.33 to 0.8 mol.

For example, in the case where the component (I) is the mixture (a) alone of (i), the polyisocyanate compound (b) is about 0.3 mol to 0.7 mol with respect to 1 mol of the mixture (a), Preferably about 0.33 mol to 0.6 mol is used.
In addition, when the component (I) is (ii) or (iii) (when the mixture (a) and glycerin are used in combination), the polyisocyanate compound (b) is further added according to the number of moles of glycerin used together. It is preferable to increase the amount used. The amount of the polyisocyanate compound (b) to be increased is preferably in the range of about half to 1 times the number of moles of glycerin used. For example, when glycerin is used in combination at a ratio of about 0 to 0.3 mol, preferably about 0 to 0.2 mol, relative to 1 mol of the mixture (a), the polyisocyanate compound (b) (preferably The amount of diisocyanate compound alone or a combination of diisocyanate compound and triisocyanate compound) is about 0 to 0.3 mol, more preferably about 0 to 0.2 mol, per 1 mol of the mixture (a). It is a ratio. In addition, when the (meth) acrylate of C2-C5 aliphatic poly (2-4) ol has a hydroxyl group, the polyisocyanate compound (b) is increased so that the equivalent number of NCO corresponding to the equivalent number of the hydroxyl group is obtained. It is preferable to do this. Usually, the total equivalent number of active hydrogen groups of each component in the mixture (a) is the same as the NCO equivalent number of the polyisocyanate compound (b) to be reacted, or the NCO equivalent number is within 0.1%. It is preferable to react in an excessive amount.
In this specification, 1 mole of the mixture (a) is the content ratio (number of moles) of each component in the mixture (a) to the total amount of the mixture (a) (sum of the number of moles of each component). It is a value when the sum of values calculated by multiplying the respective molecular weights is defined as the molecular weight of the mixture (a).

The (meth) acrylate of the C2-C5 aliphatic poly (2-4) ol used in (iii) of (I) includes C2-C5 aliphatic poly (2) such as ethylene glycol, propylene glycol and pentaerythritol. 4) (Meth) acrylate obtained by reaction of ol with (meth) acrylic acid can be mentioned. The (meth) acrylate preferably contains 30 to 100% by mass, preferably 50 to 100% by mass of the (meth) acrylate having a hydroxyl group with respect to the total amount of the (meth) acrylate (the remainder being a hydroxyl group) Acrylate of C2-C5 aliphatic poly (2-4) ol). Preferred are hydroxyethyl (meth) acrylate, poly (2-4) (meth) acrylate of pentaerythritol (preferably, a mixture of pentaerythritol di- or tri (meth) acrylate and pentaerythritol tetra (meth) acrylate), Preferably, hydroxyethyl acrylate or a mixture of pentaerythritol tri and tetraacrylate (for example, mixing ratio (mass) tri: tetra = 1: 0.01 to 1, preferably 1: 0.1 to 0.6). be able to.

The reaction of the component (I) containing the mixture (a) and the polyisocyanate (b) of (II) can be carried out in the same manner as in a normal urethanization reaction. The reaction may be performed in the presence of an inert organic solvent, for example, a ketone solvent such as butanone and a catalyst, if necessary.
The reaction temperature is usually in the range of 30 to 150 ° C., preferably 50 to 100 ° C. The end point of the reaction was calculated by a method in which the residual isocyanate group (NCO) content was reacted with excess n-butylamine and back titrated with 1N hydrochloric acid, and the residual isocyanate group (NCO) content was determined based on the polyisocyanate (b ) Is 0.5% or less, preferably 0.1% or less, based on the isocyanate group (NCO) content.

A catalyst may be added for the purpose of shortening the reaction time. As this catalyst, either a basic catalyst or an acidic catalyst is used.
Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphine such as tributylphosphine and triphenylphosphine.
Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, titanium tetrabutoxide, zirconium tetrabutoxide, and other metal alkoxides, aluminum chloride and other Lewis acids, and 2-ethylhexanoic acid tin. , Tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. An acidic catalyst of a tin compound is preferable, and dibutyltin dilaurate is more preferable.
The addition amount of these catalysts is 0.1 mass part or more normally 1 mass part or less with respect to 100 mass parts of polyisocyanate compounds (b).

Further, during the reaction, a polymerization inhibitor (for example, 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5 to prevent polymerization during the reaction) -Dihydroxy-p-benzoquinone, phenothiazine, etc.) is preferably used, and the amount of the polymerization inhibitor used is 0.01% by mass or more and 1% by mass or less, preferably 0.05% by mass with respect to the reaction mixture. It is 0.5 mass% or less.

The urethane (meth) acrylate compound (A) obtained as described above is obtained not as a single urethane compound but as a mixture of urethane compounds having different degrees of polymerization and the like, like a polymer compound. In particular, when the poly (meth) acrylate mixture (a) is reacted with the polyisocyanate compound (b) in the presence of glycerin and (meth) acrylate of C2 to C5 aliphatic poly (2 to 4) ol. This product becomes a complex polycondensate mixture (urethane (meth) acrylate compound).
The resulting urethane (meth) acrylate compound (A) has a viscosity (60 ° C.) of about 5 to 40 Pa · s, preferably about 10 to 38 Pa · s, more preferably about 12 to 38 Pa · s, and most preferably 14 to It is about 35 Pa · s. Further, among the most preferable, the curling property is less when the viscosity is 15 Pa · s or more, the curling property is further less when the viscosity is 17 Pa · s or more, and the curling property is the least when 18 Pa · s or more.
The weight average molecular weight (Mw) is about 3,000 to 50,000, preferably about 4,000 to 35,000, more preferably about 4,500 to 35,000, and still more preferably 5,000 to 35,000. About 000. In order to obtain a cured film with less curl, the weight average molecular weight is about 7,000 to 50,000, preferably about 7,000 to 35,000.
The number average molecular weight is about 1,400 to 2,500, preferably about 1,500 to 2,300, more preferably about 1,600 to 2,300, and still more preferably about 1,700 to 2,300. Most preferably, it is about 1,700 to 2,100.
One of the more preferred embodiments of the urethane (meth) acrylate compound (A) is that the weight average molecular weight is about 4,500 to 35,000, the number average molecular weight is about 1,500 to 2,300, and the viscosity (60 ° C.) is. 5 to 40 Pa · s. Further, in a more preferred embodiment, the weight average molecular weight is about 7,000 to 35,000, the number average molecular weight is about 1,700 to 2,300, and the viscosity (60 ° C.) is about 12 to 35 Pa · s. It is.

The urethane (meth) acrylate compound of the present invention is usually a urethane-modified (meth) acrylate (urethane (meth) acrylate) at a ratio calculated from the area ratio of HPLC and GPC (gel permeation chromatography). Is about 60 to 90%, preferably about 60 to 85%, and the remainder is about 10 to 40%, preferably about 15 to 40%, of non-urethane (meth) acrylate (unreacted diester derived from raw materials). It contains pentaerythritol hexa (meth) acrylate and non-urethaneized pentaerythritol multimers (multimers of tri or higher).
Reaction of the poly (meth) acrylate mixture (a) with the bifunctional polyisocyanate compound (b) (diisocyanate compound) without the presence of glycerin and (meth) acrylate of C2-C5 aliphatic poly (2-4) ol When it is made, it becomes a urethane (meth) acrylate compound (A1) represented by the following formula (1).

In the formula, X represents an isocyanate residue, n represents an integer of 0 to 100, and A, B, and Y represent an organic group represented by the following general formula (2).

(1) In the case of Y, X is an isocyanate residue, a and b and c are positive integers, a + b + c = 4, 1 ≦ a ≦ 4, 0 ≦ b ≦ 3, 0 ≦ c ≦ 3, Y is a divalent group,
(2) In the case of A or when B is present at the end, c is 0, X is an isocyanate residue, a and b are integers of 1 ≦ a ≦ 5, 0 ≦ b ≦ 4, And a + b = 5,
(3) When B is present other than at the end, c is 0, X is an isocyanate residue, a and b are integers of 1 ≦ a ≦ 4, 0 ≦ b ≦ 3, and a + b = 4 It is. However, when B is present at a position other than the terminal, it is theoretically possible that B represents the same group as Y independently of Y, but in the present specification, for the sake of simplification, it is represented as described above. .
Therefore, in the case of Y and in the case where B is present at a position other than the terminal, the general formula (2) is a divalent group, and in the case of A and when B is present at the terminal, each independently The general formula (2) is a monovalent group.
In the case of the above (2) (in the case of A or B is present at the terminal), the formula (2) can be represented by the following formula (2a).

In the formula, a ′ and b ′ are positive integers, and a ′ + b ′ = 5, 1 ≦ a ′ ≦ 5, and 0 ≦ b ′ ≦ 4.

The resin composition of the present invention contains the urethane (meth) acrylate compound (A) of the present invention and a photopolymerization initiator (C), and if necessary, (meth) acrylate (B), a curing accelerator. (D), diluent (E), and other components may be contained.
Examples of other components include a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, and a crosslinking agent.
The resin composition of the present invention is a photosensitive resin composition and can be cured by irradiating energy rays such as ultraviolet rays.
Moreover, it is preferable that the resin composition of this invention contains the organic solvent as a diluent (E) so that it can be easily made into film | membrane forms, such as a hard coat.

In the resin composition of the present invention, the content of the urethane (meth) acrylate compound (A) of the present invention is usually 5 to 97% by mass when the solid content of the resin composition of the present invention is 100% by mass, The amount is preferably 20 to 80% by mass, and in some cases, preferably about 40 to 95% by mass, more preferably about 50 to 95% by mass, and more preferably about 70 to 95% by mass.
The content of the urethane (meth) acrylate compound (A) with respect to the total amount of the resin composition of the present invention is usually 5 to 97% by mass, preferably about 20 to 95% by mass, and more preferably 40 to 95%. It is about mass%, more preferably about 45 to 95%.

Examples of the (meth) acrylate (B) that can be used in the present invention include (meth) acrylate compounds other than the urethane (meth) acrylate compound (A). For example, mono (meth) acrylate (acrylate having one acryloyl group) or polyacrylate (bifunctional (meth) acrylate or trifunctional or higher (meth) acrylate: acrylate having two or more acryloyl groups) It is. Examples of the polyacrylate include polyester (meth) acrylate, urethane (meth) acrylate oligomer (excluding the urethane (meth) acrylate compound (A)), polyester (meth) acrylate oligomer, and epoxy (meth) acrylate oligomer. Including. You may use these individually or in mixture of 2 or more types.
In the present invention, a poly (meth) acrylate compound having 2 to 6 (meth) acryloyl groups is preferred. Preferred poly (meth) acrylate compounds include C1-C12 aliphatic glycol di (meth) acrylate or dipentaerythritol poly (3-6) (meth) acrylate, more preferably C1-C12 aliphatic glycol. Mention may be made of diacrylate or dipentaerythritol poly (3-6) acrylate.
The C1-C12 aliphatic glycol diacrylate is preferably C1-C6 aliphatic glycol diacrylate.
When it is desired to obtain a flexible film, C1-C12 aliphatic glycol diacrylate is preferred, and when a hardened product is desired, dipentaerythritol poly (3-6) acrylate is preferred.
In the present invention, expressions such as “(meth) acrylate” indicate that there may be meta. For example, “(meth) acrylate” is used in the meaning of acrylate or methacrylate. In addition, expressions such as “poly (3 to 6)” or “poly (2 to 4)” mean that “poly” is “3 to 6” or “2 to 4” and the like.

Examples of mono (meth) acrylates include acryloylmorpholine; hydroxyl group-containing (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; cyclohexane-1,4-dimethanol mono (meta) ) Aliphatic (meth) such as acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Acrylate, phenoxyethyl (meth) acrylate, phenyl (poly) ethoxy (meth) acrylate, 4-cumylphenoxyethyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate Aromatic (meth) acrylates such as rate, phenylthioethyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate, and phenylphenol epoxy (meth) acrylate Can be mentioned.

Bifunctional (meth) acrylates include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (Meth) acrylate, bisphenol A (poly) ethoxy di (meth) acrylate, bisphenol A (poly) propoxy di (meth) acrylate, bisphenol F (poly) ethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, (poly) ethylene Di (meth) acrylate of ε-caprolactone adduct of glycol di (meth) acrylate hydroxybivalate neopentyl glycol (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), bisphenol And the like epoxy acrylates such as Le A diepoxy acrylate.

As trifunctional or more polyfunctional (meth) acrylates, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, trimethylolpropane (poly) ethoxytri (meth) Poly (meth) acrylates of methylols such as acrylate, trimethylolpropane (poly) propoxytri (meth) acrylate, trimethylolpropane (poly) ethoxy (poly) propoxytri (meth) acrylate; pentaerythritol tri (meth) acrylate, Pentaerythritol (poly) ethoxytetra (meth) acrylate, pentaerythritol (poly) propoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate Poly (meth) acrylates of erythritols such as relate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; tris [(meth) acryloyloxyethyl] isocyanurate And poly (meth) acrylate isocyanurates such as caprolactone-modified tris [(meth) acryloyloxyethyl] isocyanurate;

Examples of (poly) ester (meth) acrylate include di (meth) acrylate of (poly) ester diol.
(Poly) ester diol can be obtained by reaction of a diol compound with a dibasic acid or an anhydride thereof.
Examples of the diol compound include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, (poly) ethylene glycol, (poly) propylene glycol, 1,4- Butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4- Linear or branched alkyl diols such as diethyl-1,5-pentanediol and 2-butyl-2-ethyl-1,3-propanediol; alicyclic alkyl diols such as cyclohexane-1,4-dimethanol; Bisphenol A (poly) ethoxy All, or it can be exemplified bisphenol A (poly) propoxy diol.
Examples of the dibasic acid or anhydride thereof include succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, and anhydrides thereof.

Examples of the urethane (meth) acrylate oligomer include a urethane (meth) acrylate oligomer obtained by adding a hydroxyl group-containing (meth) acrylate to a reaction product of a diol compound (including the polyester diol) and an organic polyisocyanate. (However, the urethane (meth) acrylate compound (A) is excluded).
Examples of the diol compound include (poly) ethylene glycol (for example, ethylene glycol, diethylene glycol, triethylene glycol, or polyethylene glycol having a higher degree of polymerization) and (poly) propylene glycol (for example, propylene glycol, dipropylene glycol, tripropylene glycol). Or propylene glycol having a higher degree of polymerization), 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8 -Octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-di C1- such as methanol 12 aliphatic glycols or poly (C2-C4 alkylene) glycols; bisphenol A (poly) C2-C3 alkoxy diols such as bisphenol A (poly) ethoxydiol or bisphenol A (poly) propoxydiol; And polyester diol which is a reaction product with a basic acid or an anhydride thereof. Examples of the dibasic acid or anhydride thereof include succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, and anhydrides thereof.

Examples of the organic polyisocyanate used for the synthesis of the urethane (meth) acrylate oligomer include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. Linear saturated hydrocarbon isocyanates such as: isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate; 4-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4-pheni And the like can be given; down diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, aromatic polyisocyanates such as 1,5-naphthalene diisocyanate.

As said (poly) ester (meth) acrylate oligomer, the (poly) ester (meth) acrylate oligomer etc. which are obtained by reaction of said (poly) ester diol and (meth) acrylic acid etc. are mentioned, for example.
Moreover, as an epoxy (meth) acrylate oligomer, the epoxy (meth) acrylate oligomer obtained by reaction with an epoxy resin and (meth) acrylic acid is mentioned. The epoxy resin used here is preferably an epoxy resin having a plurality of epoxy groups such as bisphenol A epoxy resin.

In the resin composition of the present invention, the content of the (meth) acrylate (B) is usually 0% by mass to 94% by mass when the solid content of the resin composition of the present invention is 100% by mass. Or less, preferably 0 to 60% by mass, and may be larger than zero when used, but preferably 5 to 60% by mass, preferably 10 to 60% by mass. In some cases, 20 to 80% by mass is also preferable.
In addition, the content of (meth) acrylate (B) with respect to the total amount of the resin composition of the present invention is usually 0 to 50% by mass, preferably about 0 to 40% by mass, more preferably about 0 to 30% by mass. When used, it may be larger than zero, but is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 5 to 30% by mass.

Examples of the photopolymerization initiator (C) used in the resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy -2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one and other acetophenones; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone and other anthraquinones Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4 ′ Benzophenones such as bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Specifically, from the market, Irgacure ^RTM 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopro manufactured by Ciba Specialty Chemicals, Inc. Pan-1-one), Lucylin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) manufactured by BASF, etc. are easily available. Moreover, you may use these individually or in mixture of 2 or more types. Among these, a photopolymerization initiator belonging to acetophenones is preferable, and 1-hydroxycyclohexyl phenyl ketone (Irgacure ^RTM ) is more preferable.

In the resin composition of the present invention, the content of the photopolymerization initiator (C) is 0.1% by mass or more and 10% by mass or less when the solid content of the resin composition of the present invention is 100% by mass, Preferably they are 1 mass% or more and 7 mass% or less.
Further, the content of the photopolymerization initiator (C) relative to 100% by mass of the solid content of the resin composition of the present invention may be about 0.2 to 12% by mass. In this case, it is preferably about 0.5 to 10% by mass, more preferably about 1 to 10% by mass, and further preferably about 2 to 8% by mass.

Also, the photopolymerization initiator (C) can be used in combination with a curing accelerator (D). Examples of the curing accelerator (D) that can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, 4-dimethylaminobenzoic acid isoamyl ester, amines such as EPA, And hydrogen donors such as 2-mercaptobenzothiazole. The amount of these curing accelerators used is 0% by mass or more and 5% by mass or less when the solid content of the resin composition of the present invention is 100% by mass. You may use these individually or in mixture of 2 or more types.

In the resin composition of the present invention, a diluent (E) can be used as necessary. As the diluent (E), a normal temperature (20 ° C.) liquid solvent, usually an organic solvent, is used. For example, lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone; dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Ethers such as diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; carbonates such as ethylene carbonate and propylene carbonate Class: methyl ethyl ketone (2-butanone), methyl Ketones such as sobutyl ketone, cyclohexanone, acetophenone; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate Esters such as toluene; hydrocarbons such as xylene, diethylbenzene and cyclohexane; halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochlorobenzene; petroleum solvents such as petroleum ether and petroleum naphtha, 2H, 3H-tetra Fluoroalcohols such as fluoropropanol, hydrofluores such as perfluorobutyl methyl ether and perfluorobutyl ethyl ether Low ethers; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol; diacetone alcohol having both the performance of ketone and alcohol. You may use these individually or in mixture of 2 or more types.
Among these, ester solvents such as ethyl acetate (preferably acetate esters of C2-3 alcohol) and ketones (ketone solvents) are preferable, and C3-C6 aliphatic ketones are more preferable.

In the resin composition of the present invention, the content of the diluent (E) is in the range of about 0 to 90% by mass, preferably about 0 to 80% by mass, more preferably the total amount of the resin composition of the present invention. It is about 0 to 60% by mass.
When the solid content of the resin composition of the present invention is 100% by mass, the content of the diluent (E) is about 0 to 300% by mass, preferably 0 to 200% by mass, more preferably 0 to About 150% by mass.
In the present specification, the content of the component of the composition, for example, the content expressed by including “0 to 90% by mass” and 0 as described above does not include the component or is greater than 0 and is 90% by mass. It is meant to be included in the following range.

Furthermore, the resin composition of the present invention may be prepared by adding a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, as necessary, in addition to the above-mentioned additives. Etc. can be contained. By including them, each intended functionality can be imparted.
Fluorine compounds, silicone compounds, acrylic compounds, etc. as leveling agents, benzotriazole compounds, benzophenone compounds, triazine compounds, etc. as UV absorbers, hindered amine compounds, benzoate compounds as light stabilizers Compounds, antioxidants such as phenolic compounds, polymerization inhibitors include methoquinone, methylhydroquinone, hydroquinone and the like, and crosslinking agents include the polyisocyanates and melamine compounds.

One of the preferable resin compositions of the present invention contains the urethane (meth) acrylate compound (A) of the present invention and a photopolymerization initiator (C), and further comprises (meth) acrylate (B) or a diluent ( It is a resin composition containing at least any one of E).
More specifically, preferred resin compositions of the present invention are as follows. The composition ratio is a ratio relative to the solid content of the resin composition of 100% by mass.
(I) 5 to 97% by mass of the urethane (meth) acrylate compound (A),
0.5 to 12% by mass of the photopolymerization initiator (C),
A resin composition containing 0 to 50% by mass of (meth) acrylate (B), the diluent (E) being an organic solvent, and 0 to 300% by mass of the organic solvent.
(Ii) The resin composition as described in (i) above, containing 40 to 95% by mass of the urethane (meth) acrylate compound (A).
(Iii) The above (i) or (ii) containing 5 to 40% by mass of (meth) acrylate (B) or 50 to 150% by mass of an organic solvent which is a diluent (E) ).
(Iv) The urethane according to any one of (1) to (4), (5), (10), (12) to (16) and (19), wherein the urethane (meth) acrylate compound (A) is The (meth) acrylate compound (A) or the urethane (meth) acrylate compound (A) produced by the production method according to any one of (5), (7) or (11) above ( The resin composition according to any one of i) to (iii).
(V) The resin composition according to any one of the above (i) to (iv), wherein the photopolymerization initiator (C) is a photopolymerization initiator belonging to acetophenones.
(Vi) Any of the above (i) to (v), wherein the (meth) acrylate (B) is a C1-C12 aliphatic glycol di (meth) acrylate or dipentaerythritol poly (3-6) (meth) acrylate The resin composition according to one item.
(Vii) The resin composition according to any one of (i) to (vi) above, wherein the diluent (E) is a ketone solvent.

The resin composition of the present invention is particularly useful as a resin composition (hard coat agent) for hard coating, and can be used as a molding material for electrical product parts and electronic parts described later.
In the resin composition of the present invention, the component (A) and the component (C), and the component (B), the component (D), the component (E) and other components are mixed in any order as necessary. Can be obtained.
The hard coat of this invention can be obtained by apply | coating the resin composition of this invention on a base material, drying as needed, and irradiating the formed thin film with an ultraviolet-ray, and forming a cured film.
More specifically, the film thickness after drying the above resin composition using a bar coater or the like may be 0.1 μm or more and 300 μm or less, usually 0.1 μm or more and 50 μm or less, more preferably 1 μm. It can be obtained by coating to a thickness of 20 μm or less, drying as necessary, and irradiating with ultraviolet rays to form a cured film.
The film thickness after curing varies depending on the application, and the film thickness after curing is about 0.1 to 300 μm, preferably about 1 to 250 μm. In the case of forming a coating film on the base film, the film thickness after curing is usually 0.1 μm or more and 50 μm or less, preferably 1 μm or more and 20 μm or less, more preferably 10 μm or less, and further preferably 7 μm or less.

Examples of the base film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetyl cellulose, polyether sulfone, and cycloolefin polymer. The film to be used may be one provided with a handle or an easy adhesion layer, one subjected to surface treatment such as corona treatment, or one subjected to release treatment.

Examples of the coating method of the resin composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, micro reverse gravure coater, and die coater. Examples include coating, dip coating, spin coating, and spray coating.

Although ultraviolet rays are irradiated for curing, an electron beam or the like can also be used. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the light amount, the arrangement of the light source, etc. are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a conveyance speed of 5 to 60 m / min for one lamp having an energy of 80 to 120 W / cm ² . On the other hand, when curing with an electron beam, it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV, and the photopolymerization initiator (C) may not be used.

The cured film of the resin composition of the present invention has adhesiveness to a substrate, hardness, and appropriate flexibility, so that it can be suitably used as a display device material. For example, spacers used for LCD, EL, rear projection display, color filter materials used for electronic paper, partition material LCD, FED (SED), etc. for separating fine display elements used for PDP, electronic paper, etc. (Thing which plays a role like a pillar for maintaining a gap) or a solid-state imaging device such as a digital camera. The cured product of the photosensitive resin composition of the present invention is a resin particularly suitable for a color filter such as a liquid crystal display device or a solid-state imaging device such as a digital camera, and among these, it is particularly suitable as a color filter. This color filter has a plurality of patterned colored pixels made of a cured product of the photosensitive resin composition of the present invention prepared as described above, or a black matrix and a photo spacer.

In the present invention, when the display device is a liquid crystal display device, for example, a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter using the photosensitive resin composition of the present invention, a polarized light A film or the like is produced in a laminated structure in this order. Taking a solid-state imaging device as an example, for example, a color filter layer using the photosensitive resin composition of the present invention is provided on a silicon wafer provided with transfer electrodes and photodiodes, and then a microlens is laminated. It is produced by this.

As other uses of the photosensitive resin composition of the present invention, it can be used, for example, in printing inks, paints, adhesives, liquid resist inks, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. Moreover, unless otherwise indicated in an Example, a part shows a mass part. In the examples, the abbreviations used are as follows.
DPETtriA: Dipentaerythritol triacrylate
DPETtetraA: Dipentaerythritol tetraacrylate
DPETpentaA: Dipentaerythritol pentaacrylate
DPEThexaA: Dipentaerythritol hexaacrylate and
TPETA: acrylate HPLC of higher polymer than tripentaerythritol HPLC: high performance liquid chromatography GPC: gel permeation chromatography The HPLC and GPC measurement conditions are as follows.
HPLC measurement equipment: SHIMADZU LC-10AD, SCL-10A, SPD-10A, CTO-10A, DGU-14A
Detector: UV 254nm
Column: GL Science Inert Sil ODS-2 (4.6 x 150 mm)
Column temperature: 40 ° C
Eluent: Acetonitrile / 0.1wt% H ₃ PO ₄ = 60/40
Flow rate: 0.6ml / min.
Sample injection volume: 2 μl
Sample concentration: 1 wt%

GPC measurement condition equipment: TOSOH HLC-8220 GPC
Detector: RI
Column: TOSOH TSK-GEL SUPER HZM-N
Column temperature: 40 ° C
Eluent: THF
Flow rate: 0.35ml / min.
Sample injection volume: 5 μl
Sample concentration: 1 wt%

Raw material synthesis example 1
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 449.7 g (6.2 mol) of acrylic acid, 9 of sulfuric acid .81 g, cupric chloride 1.03 g and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling off the produced water with the solvent. After the reaction, 849.4 g of toluene was added for dilution, neutralized with 25% aqueous NaOH solution, and then washed 3 times with 600 g of 15% by mass brine. The solvent was distilled off under reduced pressure to obtain 538.9 g of a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 80 mg KOH / g, hydroxyl equivalent (active hydrogen group equivalent): 701.4 g / Eq).
The ratio of each component of DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the area ratio (%) of high performance liquid chromatography (HPLC) was 10: 43: 37: 10. The viscosity of the mixture was 6,300 mPa · s (25 ° C.).

Raw material synthesis example 2
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 432.4 g (6.0 mol) of acrylic acid, 9 of sulfuric acid .81 g, cupric chloride 0.99 g, and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling the produced water with the solvent. After the reaction, 849.4 g of toluene was added for dilution, neutralized with 25% aqueous NaOH solution, and then washed 3 times with 600 g of 15% by mass brine. The solvent was distilled off under reduced pressure to obtain 525.3 g of a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 92 mg KOH / g, hydroxyl equivalent: 609.9 g / Eq).
The ratio of each component of DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the HPLC area ratio (%) was 12: 45: 36: 7. The viscosity of the mixture was 6,300 mPa · s (25 ° C.).

Raw material synthesis example 3
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 402.1 g (5.6 mol) of acrylic acid, and sulfuric acid 9 .81 g, cupric chloride 0.92 g, and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling off the produced water with the solvent. After the reaction, 849.4 g of toluene was added for dilution, neutralized with 25% aqueous NaOH solution, and then washed 3 times with 600 g of 15% by mass brine. The solvent was distilled off under reduced pressure to obtain 494.9 g of a mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 120 mgKOH / g, hydroxyl equivalent: 467.6 g / Eq).
The ratio of each component of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the area ratio (%) of HPLC was 3: 26: 41: 24: 6. The viscosity of the mixture was 6,000 mPa · s (25 ° C.).

Comparative raw material synthesis example 1
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 497.2 g (6.9 mol) of acrylic acid, 9 of sulfuric acid 9 .81 g, cupric chloride 1.14 g, and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling off the produced water with the solvent. After the reaction, 849.4 g of toluene was added for dilution, neutralized with 25% aqueous NaOH solution, and then washed 3 times with 600 g of 15% by mass brine. The solvent was distilled off under reduced pressure to obtain 590.1 g of a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 45 mg KOH / g, hydroxyl equivalent: 1246.9 g / Eq).
The ratio of each component of DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the HPLC area ratio (%) was 2: 30: 56: 12. The viscosity of the mixture was 6,500 mPa · s (25 ° C.).

Comparative raw material synthesis example 2
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, 254.3 g (1.0 mol) of dipentaerythritol, 380.5 g (5.3 mol) of acrylic acid, 9 of sulfuric acid .81 g, cupric chloride 0.88 g, and toluene 424.7 g were charged, and the reactor was heated and reacted for 12 hours while azeotropically distilling the produced water with the solvent. After the reaction, 849.4 g of toluene was added for dilution, neutralized with 25% aqueous NaOH solution, and then washed 3 times with 600 g of 15% by mass brine. The solvent was distilled off under reduced pressure to obtain 480.1 g of a mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 140 mgKOH / g, hydroxyl equivalent: 400.8 g / Eq).
The ratio of each component of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the HPLC area ratio (%) was 4: 30: 42: 19: 5. The viscosity of the mixture was 5,800 mPa · s (25 ° C.).

Example A (Synthesis Example 1)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 1 (hydroxyl value: 80 mgKOH / g, hydroxyl group equivalent: 701) in a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller. .4 g / Eq) 446.47 g (0.64 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform. Was 50 ° C. Subsequently, 53.53 g (0.32 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and after the addition, the mixture was reacted at 80 ° C. for 6 hours, so that the NCO content was 0.1% or less. As a result, the urethane acrylate of the present invention was obtained.
This was an average molecular weight (Mw = 4,500, Mn = 1,500) and a viscosity of 6 Pa · s (60 ° C.).
Moreover, when the component was confirmed about the obtained urethane acrylate by HPLC and GPC, the content of urethane acrylate is 64% (ratio with respect to the total amount), and the acrylate which is not urethanized (unreacted DPEThexaA and by-product) The content of the acrylate of the pentaerythritol multimer, etc.) was 36%.

Example B (Synthesis Example 2)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. 9.9 g / Eq) 439.41 g (0.72 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor, and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst, and stirred until uniform. Was 50 ° C. Subsequently, 60.59 g (0.36 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and the mixture was reacted at 80 ° C. for 6 hours, so that the NCO content was 0.1% or less. As a result, urethane acrylate was obtained.
This was an average molecular weight (Mw = 5,500, Mn = 1,800) and a viscosity of 11 Pa · s (60 ° C.).
Further, the obtained urethane acrylate had a urethane acrylate content of 74% (ratio to the total amount) and an urethanized acrylate content of 26%.

Example C (Synthesis Example 3)
A mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 3 (hydroxyl value: 120 mgKOH / g, hydroxyl group equivalent: in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. 467.6 g / Eq) 423.78 g (0.91 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform. The temperature was 50 ° C. Subsequently, 76.22 g (0.45 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and after the addition, the mixture was reacted at 80 ° C. for 6 hours. The NCO content was 0.1% or less. As a result, urethane acrylate was obtained.
This was an average molecular weight (Mw = 7,800, Mn = 1,700) and a viscosity of 16 Pa · s (60 ° C.).
Further, the obtained urethane acrylate had a urethane acrylate content of 73% (ratio to the total amount) and an urethanized acrylate content of 27%.

Example D (Synthesis Example 4)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. .9 g / Eq) 340.10 g (0.56 mol), glycerin 4.08 g (0.04 mol), 2-butanone 100.00 g, 4-methoxyphenol 0.20 g as a polymerization inhibitor, and urethanization reaction catalyst Dibutyltin dilaurate 0.20 g was added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 55.83 g (0.33 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and after the addition, the mixture was reacted at 80 ° C. for 6 hours. The NCO content was 0.1% or less. This was the end point of the reaction. By heating to 60 ° C., the solvent (2-butanone) was distilled off under reduced pressure to obtain the urethane acrylate of the present invention.
This was an average molecular weight (Mw = 10,300, Mn = 1,800) and a viscosity of 18 Pa · s (60 ° C.).
Further, the obtained urethane acrylate had a urethane acrylate content of 74% (ratio to the total amount) and an urethanized acrylate content of 26%.

Example E (Synthesis Example 5)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. 2.9 g / Eq) 308.78 g (0.51 mol), mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by weight mixing ratio: 70/30, hydroxyl group equivalent: 421.9 g / Eq) 29.06 g (0 0.07 mol), 4.23 g (0.05 mol) of glycerol, 100.00 g of 2-butanone, 0.20 g of 4-methoxyphenol as a polymerization inhibitor, and 0.20 g of dibutyltin dilaurate as a urethanization reaction catalyst The mixture was stirred until the internal temperature reached 50 ° C. Subsequently, 57.93 g (0.34 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and after the addition, the mixture was reacted at 80 ° C. for 6 hours. The NCO content was 0.1% or less. This was the end point of the reaction. By heating to 60 ° C., the solvent (2-butanone) was distilled off under reduced pressure to obtain the urethane acrylate of the present invention.
This was an average molecular weight (Mw = 11,300, Mn = 1,700) and a viscosity of 17 Pa · s (60 ° C.).
Further, the obtained urethane acrylate had a urethane acrylate content of 74% (ratio to the total amount) and an urethanized acrylate content of 26%.

Example F (Synthesis Example 6)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. .9 g / Eq) 325.95 g (0.53 mol), 2-hydroxyethyl acrylate 8.44 g (0.07 mol), glycerin 4.46 g (0.05 mol), 2-butanone 100.00 g, polymerization prohibited 0.20 g of 4-methoxyphenol as an agent and 0.20 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 61.15 g (0.36 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and after the addition, the mixture was reacted at 80 ° C. for 6 hours, so that the NCO content was 0.1% or less. This was the end point of the reaction. By heating to 60 ° C., the solvent (2-butanone) was distilled off under reduced pressure to obtain the urethane acrylate of the present invention.
This was an average molecular weight (Mw = 9,500, Mn = 1,800) and a viscosity of 17 Pa · s (60 ° C.).
Further, the obtained urethane acrylate had a urethane acrylate content of 74% (ratio to the total amount) and an urethanized acrylate content of 26%.

Example G (Synthesis Example 7)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. .9 g / Eq) 320.42 g (0.53 mol), 2-hydroxyethyl acrylate 8.94 g (0.08 mol), glycerin 5.91 g (0.06 mol), 2-butanone 100.00 g, polymerization prohibited 0.20 g of 4-methoxyphenol as an agent and 0.20 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 64.73 g (0.38 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and the mixture was reacted at 80 ° C. for 6 hours. The NCO content was 0.1% or less. This was the end point of the reaction. By heating to 60 ° C., the solvent (2-butanone) was distilled off under reduced pressure to obtain the urethane acrylate of the present invention.
This was an average molecular weight (Mw = 19,700, Mn = 1,800) and a viscosity of 27 Pa · s (60 ° C.).
Further, the obtained urethane acrylate had a urethane acrylate content of 75% (ratio to the total amount) and an urethanized acrylate content of 25%.

Example H (Synthesis Example 8)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. .9 g / Eq) 330.55 g (0.54 mol), 2-butanone 100.00 g, 4-methoxyphenol 0.20 g as a polymerization inhibitor, and dibutyltin dilaurate 0.20 g as a urethanization reaction catalyst were uniformly added. The mixture was stirred until the internal temperature reached 50 ° C. Subsequently, 17.36 g (0.10 mol) of hexamethylene diisocyanate and 52.09 g (0.10 mol) of TLA-100 (hexamethylene diisocyanate trimer) were added dropwise so that the internal temperature did not exceed 80 ° C. Thereafter, the reaction was allowed to proceed at 80 ° C. for 6 hours, and the end point of the reaction was determined when the NCO content was 0.1% or less. By heating to 60 ° C., the solvent (2-butanone) was distilled off under reduced pressure to obtain the urethane acrylate of the present invention.
This was an average molecular weight (Mw = 16,300, Mn = 2,000) and a viscosity of 24 Pa · s (60 ° C.).
Further, the obtained urethane acrylate had a urethane acrylate content of 74% (ratio to the total amount) and an urethanized acrylate content of 26%.

Example I (Synthesis Example 9)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. .9 g / Eq) 337.88 g (0.55 mol), 2-butanone 100.00 g, 4-methoxyphenol 0.20 g as a polymerization inhibitor, dibutyltin dilaurate 0.20 g as a urethanization reaction catalyst, and uniformly added The mixture was stirred until the internal temperature reached 50 ° C. Subsequently, 26.62 g (0.16 mol) of hexamethylene diisocyanate and 35.50 g (0.07 mol) of TLA-100 (hexamethylene diisocyanate trimer) were added dropwise so that the internal temperature did not exceed 80 ° C. Thereafter, the reaction was allowed to proceed at 80 ° C. for 6 hours, and the end point of the reaction was determined when the NCO content was 0.1% or less. By heating to 60 ° C., the solvent (2-butanone) was distilled off under reduced pressure to obtain the urethane acrylate of the present invention.
This was an average molecular weight (Mw = 8,500, Mn = 1,800) and a viscosity of 12 Pa · s (60 ° C.).
Further, the obtained urethane acrylate had a urethane acrylate content of 74% (ratio to the total amount) and an urethanized acrylate content of 26%.

Example J (Synthesis Example 10)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 1 (hydroxyl value: 80 mgKOH / g, hydroxyl group equivalent: 701) in a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller. .4 g / Eq) 331.80 g (0.54 mol), 2-butanone 100.00 g, 4-methoxyphenol 0.20 g as a polymerization inhibitor, dibutyltin dilaurate 0.20 g as a urethanization reaction catalyst, and uniformly added The mixture was stirred until the internal temperature reached 50 ° C. Subsequently, 7.58 g (0.05 mol) of hexamethylene diisocyanate and 60.62 g (0.12 mol) of TLA-100 (hexamethylene diisocyanate trimer) were added dropwise so that the internal temperature did not exceed 80 ° C. Thereafter, the reaction was allowed to proceed at 80 ° C. for 6 hours, and the end point of the reaction was determined when the NCO content was 0.1% or less. By heating to 60 ° C., the solvent (2-butanone) was distilled off under reduced pressure to obtain the urethane acrylate of the present invention.
This was an average molecular weight (Mw = 11,700, Mn = 1,800) and a viscosity of 23 Pa · s (60 ° C.).
The urethane acrylate thus obtained had a urethane acrylate content of 66% (ratio to the total amount) and a non-urethane acrylate content of 34%.

Example K (Synthesis Example 11)
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 3 (hydroxyl value: 120 mgKOH / g, hydroxyl group equivalent: 467) in a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller. .6 g / Eq) 305.74 g (0.50 mol), 2-butanone 100.00 g, 4-methoxyphenol 0.20 g as a polymerization inhibitor, dibutyltin dilaurate 0.20 g as a urethanization reaction catalyst, and uniformly added The mixture was stirred until the internal temperature reached 50 ° C. Subsequently, 10.47 g (0.06 mol) of hexamethylene diisocyanate and 83.79 g (0.17 mol) of TLA-100 (hexamethylene diisocyanate trimer) were added dropwise so that the internal temperature did not exceed 80 ° C. Thereafter, the reaction was allowed to proceed at 80 ° C. for 6 hours, and the end point of the reaction was determined when the NCO content was 0.1% or less. By heating to 60 ° C., the solvent (2-butanone) was distilled off under reduced pressure to obtain the urethane acrylate of the present invention.
This was an average molecular weight (Mw = 27,700, Mn = 2,000) and a viscosity of 32 Pa · s (60 ° C.).
In addition, the urethane acrylate thus obtained had a urethane acrylate content of 74% (ratio to the total amount) and an urethanized acrylate content of 26%.

Comparative Synthesis Example 1
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Comparative Raw Material Synthesis Example 1 (hydroxyl value: 45 mgKOH / g, hydroxyl equivalent) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. : 1246.9 g / Eq) 473.39 g (0.38 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor, 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst, and stirred until uniform. The internal temperature was 50 ° C. Subsequently, 26.61 g (0.16 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and after the addition, the mixture was reacted at 80 ° C. for 6 hours, so that the NCO content was 0.1% or less. As a result, urethane acrylate was obtained.
This was an average molecular weight (Mw = 2,200, Mn = 1,200) and a viscosity of 2 Pa · s (60 ° C.).
The urethane acrylate thus obtained had a urethane acrylate content of 48% (ratio to the total amount) and a non-urethane acrylate content of 52%.

Comparative Synthesis Example 2
Mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Comparative Raw Material Synthesis Example 2 (hydroxyl value: 140 mgKOH / g, hydroxyl group) in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller (Equivalent: 400.8 g / Eq) 413.28 g (1.03 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform. The internal temperature was 50 ° C. Subsequently, 86.72 g (0.52 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and the mixture was reacted at 80 ° C. for 2 hours to cause gelation. It was not obtained.

Comparative Synthesis Example 3
A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 2 (hydroxyl value: 92 mgKOH / g, hydroxyl group equivalent: 609.) in a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller. 9 g / Eq) 316.79 g (0.52 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform. The temperature was 50 ° C. Subsequently, 83.21 g (0.16 mol) of TLA-100 (hexamethylene diisocyanate trimer) was added dropwise so that the internal temperature did not exceed 80 ° C., and the mixture was reacted at 80 ° C. for 4 hours. The target urethane acrylate was not obtained.

Comparative Synthesis Example 4
A mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 3 (hydroxyl value: 120 mgKOH / g, hydroxyl group equivalent: in a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller. 467.6 g / Eq) 297.93 g (0.49 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor, and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst, and stirred until uniform. The temperature was 50 ° C. Subsequently, 102.07 g (0.20 mol) of TLA-100 (hexamethylene diisocyanate trimer) was added dropwise so that the internal temperature did not exceed 80 ° C., and the mixture was reacted at 80 ° C. for 2 hours. The target urethane acrylate was not obtained.

Examples 1 to 4 and Comparative Examples 1 to 2
Each component was mix | blended with the composition shown in Table 1, and it mixed until it became uniform, and prepared the resin composition of this invention, and the resin composition of a comparative example. Each of the obtained resin compositions was applied onto a PET film (thickness 125 μm) subjected to easy adhesion treatment by a bar coater and dried at about 80 to 100 ° C. Each of the obtained coating films was irradiated with ultraviolet rays using an ultraviolet irradiator (JAPAN STORE BATTERY CO, LTD .: CS30L-1-1) to cure the coating films. A PET film (hard coat film) having a hard coat thickness of about 5 μm was obtained.
The curing conditions are as follows.
Curing conditions: High pressure mercury lamp: 120 W / cm, lamp height: 10 cm, conveyor speed: 10 m / min (irradiation energy: about 300 mW / cm ² , about 200 mJ / cm ² ).
The unit of numerical values in Table 1 represents “parts by mass”.

(note)
* 1, DPHA: Dipentaerythritol pentaacrylate / hexaacrylate mixture * 2, MEK: Methyl ethyl ketone * 3, Irg. 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.

The following items were evaluated for the hard coat films obtained in Examples 1 to 4 and Comparative Examples 1 and 2, and the results are shown in Table 2.

(Pencil hardness)
According to JIS K 5600-5-4, the pencil hardness of the obtained hard coat film was measured using a pencil scratch tester. Specifically, on the polyester film having the cured film to be measured, the pencil is applied with a load of 750 g from the top at a 45 degree angle, and is scratched for about 5 mm. expressed.

(Adhesion)
The surface of the hard coat film obtained after the light resistance test was scratched with a cutter (with a side of 30 mm), and a cellophane tape was affixed thereon and peeled at an angle of 90 degrees.
○: No peeling ×: Peeling occurred

(Abrasion resistance)
A load of 200 g / cm ² was applied to Steel Wool # 0000, the surface of the obtained hard coat film was reciprocated 10 times, and the state of the scratch was visually confirmed.
○: No scratch ×: Scratch occurred

(curl)
The obtained hard coat film was cut into 5 cm × 5 cm, left in a drying oven at 80 ° C. for 1 hour, and then returned to room temperature. The height of each of the four sides that floated on a horizontal table was measured, and the sum of the four sides was taken as the measured value (unit: mm). At this time, the curl of the base material itself was 0 mm.

(appearance)
Surface cracks, whitening, cloudiness, etc. were judged visually.
Evaluation ○: Good ×: Significant crack occurrence

As is clear from the results in Table 2, the film having a cured film obtained by curing the resin composition of the present invention has good hardness, adhesion, and scratch resistance, and does not generate cracks. Compared with the curl is small.

Examples 5 to 7 and Comparative Example 3
Each component was mix | blended with the composition shown in Table 3, it mixed until it became uniform, and the resin composition of this invention and the resin composition of the comparative example were prepared. Each obtained resin composition was apply | coated with the bar coater on the stainless steel plate. Each obtained coating film was irradiated with ultraviolet rays by an ultraviolet irradiator (manufactured by Nippon Battery Co., Ltd.) under a nitrogen atmosphere to cure the coating film.
The thickness of each cured film obtained was about 200 μm. This cured film was peeled off from the stainless steel plate to obtain a cured film for testing.
The curing conditions are as follows.
Curing conditions: High pressure mercury lamp: 80 W / cm, lamp height: 10 cm, conveyor speed: 5 m / min (irradiation energy: about 900 mW / cm ² , about 600 mJ / cm ² ).
Moreover, the unit of numerical values in Table 3 represents “parts by mass”.

(note)
* 4, HDDA: 1,6-hexanediol diacrylate

(Tensile test)
In accordance with JIS K 7162, dumbbell-shaped test pieces were prepared from the films obtained in Examples 5 to 7 and Comparative Example 3, and the following data was measured using a tensile tester. The evaluation results are shown in Table 4.
1: Young's modulus (elastic modulus)
2: Stress at break 3: Elongation at break

As is apparent from the results in Table 4, the cured film obtained by curing the resin composition of the present invention has a high stress at break and elongation at break, and is flexible and tough compared to the comparative examples. Recognize.

Examples 8 to 15
Each component was mix | blended with the composition shown in following Table 5, and it mixed until it became uniform, and prepared the resin composition of this invention. In the table, “MEK” and “Irg.184” have the same meaning as in Table 1.
Using each of the obtained resin compositions, a PET film (hard coat film) having a hard coat with a film thickness of about 5 μm was obtained in the same manner as in Examples 1 to 4.
The obtained hard coat film was evaluated in the same manner as in Examples 1 to 4, and the results are shown in Table 6 below.

As is apparent from the results in Table 6, the film having a cured film obtained by curing the resin composition of the present invention has good hardness, adhesion, and scratch resistance, and does not generate cracks.

The cured film obtained by curing the resin composition of the present invention has good hardness, adhesion, scratch resistance, and maintains the required characteristics as a hard cord such as no occurrence of cracks, while curling is small, It is characterized by having both flexible and tough properties.

The hard coat film obtained by curing the resin composition of the present invention has good hardness, adhesion, and scratch resistance, and does not cause curling or cracking. Therefore, the resin composition of the present invention is suitable as a material for plastic films, hard coatings for small cases, color filters, black matrices, and spacers.

Claims

(I) The following (i), (ii) or (iii),
(I) including at least two selected from the group consisting of dipentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Dipentaerythritol poly (meth) acrylate mixture (a) (hereinafter referred to as the mixture (a)) having a hydroxyl value of 80 to 120 mgKOH / g, or
(Ii) both the mixture (a) and glycerin, or
(Iii) the mixture (a), glycerol and (meth) acrylates of C2-C5 aliphatic poly (2-4) ol,
Either
(II) a polyisocyanate compound (b) containing a diisocyanate compound,
Urethane (meth) acrylate compound (A) obtained by reacting with.
The urethane (meth) acrylate compound (A) according to claim 1, wherein (I) is the mixture (a) of (i).
The polyisocyanate compound (b) of (II) is a diisocyanate compound alone or a combination of a diisocyanate compound and a triisocyanate compound, and the ratio of the diisocyanate compound to the triisocyanate compound is 0 to 3 per mol of the diisocyanate compound. The urethane (meth) acrylate compound (A) according to claim 1, which has a ratio of 10 mol.
The urethane (meth) acrylate compound (A) according to claim 1 represented by the following general formula (1):

(Wherein X is an isocyanate residue, n is an integer of 0 to 100,
Y is an organic group represented by the following general formula (2), wherein a, b and c are integers of 1 ≦ a ≦ 4, 0 ≦ b ≦ 3 and 0 ≦ c ≦ 3, respectively. And a + b + c = 4,

as well as,
A is an organic group represented by the general formula (2), wherein X is an isocyanate residue, c is 0, and a and b are integers of 1 ≦ a ≦ 5 and 0 ≦ b ≦ 4 And a + b = 5,
B is an organic group represented by the general formula (2), wherein X is an isocyanate residue, c is 0, and a and b are
(I) when B is present at the end, 1 ≦ a ≦ 5, 0 ≦ b ≦ 4, and a + b = 5,
(Ii) When B is present at a position other than the end, a and b in the formula are integers of 1 ≦ a ≦ 4, 0 ≦ b ≦ 3, and a + b = 4).
(I) (i) The mixture (a) and the polyisocyanate compound (b) of (II) are mixed with the isocyanate in the polyisocyanate compound (b) with respect to 1 equivalent of active hydrogen groups in the mixture (a). The process for producing the urethane (meth) acrylate compound (A) according to claim 1, wherein the reaction is carried out at a ratio of a group equivalent of 0.1 to 50 equivalents.
The urethane (meth) acrylate compound (A) according to claim 1, wherein (I) is the mixture (a) and glycerin (ii).
The mixture (a) and glycerin of claim 1 and the polyisocyanate compound (b) of (II) of claim 1 in 1 equivalent of active hydrogen groups in the mixture (a) Method for producing urethane (meth) acrylate compound (A) to be reacted at an active hydrogen group equivalent of 0.01 to 10 equivalents and a ratio of isocyanate group equivalents of 0.1 to 50 equivalents in polyisocyanate compound (b) of (II) .
A resin composition comprising the urethane (meth) acrylate compound (A), (meth) acrylate (B) and photopolymerization initiator (C) according to claim 1.
The resin composition according to claim 8, which is used for a hard coat.
2. The urethane (meth) acrylate according to claim 1, wherein (I) is one of (iii) of the mixture (a), glycerin and (meth) acrylate of C2-C5 aliphatic poly (2-4) ol. Compound (A).
The mixture (a) of claim 1 (I) (iii), the glycerin and the (meth) acrylate of a C2-C5 aliphatic poly (2-4) ol, and (II) of claim 1 The polyisocyanate compound (b) of the glycerin active hydrogen group equivalent 0.01 to 10 equivalent and the C2 to C5 aliphatic poly (2 to 4) with respect to 1 equivalent of active hydrogen group in the mixture (a) The urethane (meta) of claim 1, wherein the reaction is carried out at a ratio of 0.01 to 10 equivalents of active hydrogen group equivalent of all (meth) acrylate and 0.1 to 50 equivalent of isocyanate group equivalent of polyisocyanate compound (b). ) A process for producing the acrylate compound (A).
The mixture (a) in (I) contains 35 to 60% of dipentaerythritol penta (meth) acrylate in the area ratio (%) of high performance liquid chromatography (HPLC) with respect to the total amount of the mixture (a). And the total of the three components including dipentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate is 90-100%, and the balance 0-10% is dipentaerythritol tri (meth) acrylate and The urethane (meth) acrylate compound (A) according to claim 1, wherein the urethane (meth) acrylate compound is a multimeric (meth) acrylate of tripentaerythritol or higher.
The urethane (meth) acrylate compound (A) according to claim 1 or 12, wherein the polyisocyanate compound (b) is a diisocyanate compound alone.
The urethane (meth) acrylate compound (A) according to claim 1 or 12, wherein the polyisocyanate compound (b) is a combination of a diisocyanate compound and a triisocyanate compound.
The urethane (meth) acrylate compound (A) according to claim 13, wherein the diisocyanate compound is hexamethylene diisocyanate.
The mixture (a) is a ternary mixture of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, or dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaacrylate. The urethane (meth) acrylate according to claim 1, which is a four-component mixture of pentaerythritol hexaacrylate, and the polyisocyanate compound (b) is hexamethylene diisocyanate alone or both hexamethylene diisocyanate and hexamethylene diisocyanate trimer. Compound (A).
A resin composition containing the urethane (meth) acrylate compound (A) according to claim 1 and a photopolymerization initiator (C).
A cured film of a resin composition containing the urethane (meth) acrylate compound (A) according to claim 1 and a photopolymerization initiator (C).
The urethane (meth) acrylate compound (A) according to claim 1, having a viscosity (60 ° C) of 5 to 40 Pa · s.