KR101664003B1 - Urethane (meth)acrylate compound and resin composition containing same - Google Patents

Abstract

(I) A urethane (meth) acrylate compound (A) obtained by reacting any one of the following (i), (ii) or (iii) with a polyisocyanate compound (b) containing a diisocyanate compound , And a resin composition containing the urethane (meth) acrylate compound (A) and the photopolymerization initiator (C), a cured product of the resin composition, a hard coating agent comprising the resin composition and a hard coating:
(i) a group consisting of dipentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (A) (hereinafter referred to as a mixture (a)) of dipentaerythritol poly (meth) acrylate mixture containing at least two selected and having a hydroxyl value of 80 to 120 mgKOH / g,
(ii) a mixture of the mixture (a) and glycerin,
(iii) the mixture of (a), (tri) of glycerine and (meth) acrylate of C2 to C5 aliphatic poly (2-4) alcohols.

Description

URETHANE (METH) ACRYLATE COMPOUND AND RESIN COMPOSITION CONTAINING SAME [0001] The present invention relates to a urethane (meth)

The present invention relates to a process for producing (meth) acrylic acid esters of the group consisting of dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (Meth) acrylate compound (A) containing at least two kinds of selected dipentaerythritol poly (meth) acrylate mixture (a) having a hydroxyl value of 80 to 120 mgKOH / g as a raw material, A resin composition comprising the urethane (meth) acrylate compound (A) and a photopolymerization initiator, and a cured film of the resin composition. The cured coating film of the resin composition of the present invention is excellent in hardness, adhesion to substrate, scratch resistance, small curl, and less cracking, and therefore is useful as a hard coating for a plastic film or a small chassis.

Since the cured coating of the resin composition of the present invention has good adhesion to a base material, has a high hardness and has appropriate flexibility, the resin composition of the present invention can be used as a color filter (for example, a color liquid crystal display, Color filters used in cameras, color digital cameras, electronic papers, etc.), black matrices, or spacers.

At present, plastics excellent in various properties such as processability, transparency, optical characteristics, and lightweight and inexpensive are utilized in industry. However, plastics have drawbacks such as being soft compared to glass and the like and easily damaged on the surface, so that coating of a hard coating agent on a plastic surface is generally performed. As the hard coating agent, a thermosetting type such as a silicone coating, an acrylic coating, and a melamine coating is widely known. Among them, silicone hard coatings have been mainly used because of their excellent performance and quality. However, the silicone-based hard coating agent has a drawback that the curing time is long and expensive.

Thus, a photosensitive acrylic hard coating agent has been developed and used as a hard coating agent that compensates for the drawbacks of silicone-based hard coating agents (see Patent Document 1). Since the acrylic hard coating agent is immediately cured by irradiation with radiation such as ultraviolet rays, the processing speed is high, and the hardness, abrasion resistance, and the like are excellent. For that reason, the acrylic hard coating agent has become mainstream in the hard coating field. Particularly, the acrylic hard coating agent is also suitable for coating the surface of the substrate during continuous processing of a base film such as polyester.

Examples of the base film of plastic include a polyester film, an acrylic film, a polycarbonate film, a vinyl chloride film, a triacetylcellulose film, and a polyethersulfone film. Among them, polyester films are most widely used because of their excellent properties. This polyester film is used as a shatterproof film for glass or a shading film for a vehicle, a surface film for a whiteboard, an antifouling film for a system kitchen surface, a CRT flat television, a touch panel, a liquid crystal display (LCD) , A plasma display (PDP), an organic EL display, and the like.

In addition to films, electronic device chassis such as the body of a home appliance, a switch, a mobile phone, a PC, and an MP3 player are widely used as a polyester resin molding. They are all hard coated to prevent damage to the surface. In addition to polyesters, hard-coated sheets or substrates such as polycarbonate or acrylic are used for liquid crystal-related members around optical discs and backlights, for example.

In recent years, a film having a function other than the performance as a hard coating called scratch resistance has been developed in the hard coat layer. For example, in a display body such as a CRT, LCD, or PDP in which a film is formed, the display screen becomes difficult to see due to reflection, and eyes are liable to be fatigued. For example, as in Patent Document 2, Hard coatings have also been developed.

On the other hand, studies have been made to improve hardness for the purpose of hard coating. For example, in Patent Document 3, the hardness is improved by adding a polyfunctional urethane acrylate to the resin composition. However, there is a problem that the polyfunctional urethane acrylate being used has a large curing shrinkage and cracks are generated.

In Patent Document 4, a polyfunctional urethane (meth) acrylate is used as a resin composition for hard coating of an antireflection material. This hard coating is considerably superior in terms of hardness, longevity and scratch resistance, but is not necessarily satisfactory, and further improvements are required.

Japanese Patent Application Laid-Open No. H09-48934 Japanese Patent Application Laid-Open No. H09-145903 Japanese Patent Application Laid-Open No. 2001-113648 Japanese Patent Application Laid-Open No. 2000-187102

It is an object of the present invention to provide a cured coating film which is excellent in hardness and scratch resistance, has less occurrence of curling or cracking, is superior to the above-mentioned known ones, and a urethane (meth) acrylate compound and a resin composition containing the same .

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems and have reached the present invention.

That is, the present invention relates to the following invention.

(Meth) acrylate compound (1) obtained by reacting (I) a polyisocyanate compound (b) containing a diisocyanate compound with either one of the following (i), (A):

(i) a group consisting of dipentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (A) (hereinafter referred to as mixture (a)) of at least two selected, and having a hydroxyl value of 80 to 120 mgKOH / g, and a dipentaerythritol poly (meth)

(ii) a mixture of the mixture (a) and glycerin,

(iii) the mixture of (a), (tri) of glycerine and (meth) acrylate of C2 to C5 aliphatic poly (2-4) alcohols.

(2) The urethane (meth) acrylate compound (A) of the above (1), wherein (I) is the mixture (a) of (i).

(3) The polyisocyanate compound (b) of the above (1) or (2), wherein the polyisocyanate compound (b) is a diisocyanate compound alone or a combination of a diisocyanate compound and a triisocyanate compound, and the ratio of the diisocyanate compound and the triisocyanate compound is (Meth) acrylate compound (A) having a triisocyanate compound in a proportion of 0 to 10 moles per mole of the diisocyanate compound,

(4) The urethane (meth) acrylate compound (A) of any one of the above-mentioned (1) to (3)

Wherein X is an isocyanate residue, n is an integer from 0 to 100,

Y is an organic group of the following formula (2): wherein a, b and c are integers of 1? A? 4, 0 b? 3 and 0? C? 3, and a + b + c = 4), and

A is an organic group represented by the following formula (2): wherein X is an isocyanate residue, c is 0, a and b are integers of 1? A? 5, 0 b? 4, and a + b = 5 ),

B is an organic group of the formula (2): wherein X is an isocyanate residue, c is 0,

(i) when B is present at the terminal, an integer of 1? a? 5, 0 b? 4, and a + b = 5,

(ii) When B is present at a terminal other than the terminal, a and b in the above formula are integers of 1? a? 4, 0 b? 3, and a + b = 4.

(5) The polyisocyanate compound (b) of the mixture (a) and the polyisocyanate compound (b) of the mixture (a) and the isocyanate compound (b) (Meth) acrylate compound (A) according to any one of (1) to (4), wherein the reaction is carried out at a ratio of 0.1 to 50 equivalents.

(6) The urethane (meth) acrylate compound (A) which is the mixture (a) and glycerin of (i) in (1) or (3) above.

(7) The polyisocyanate compound (b) of the above mixture (a) and the glycerin and the polyisocyanate compound (b) of the above (1) are mixed in an amount of 1 equivalent of the active hydrogen group in the mixture (a) (Meth) acrylate compound (A) according to (6), which is reacted in an amount of 0.01 to 10 equivalents of an active hydrogen group equivalent and 0.1 to 50 equivalents of an isocyanate group in the polyisocyanate compound (b) of the formula (II) Way.

(8) A resin composition comprising the urethane (meth) acrylate compound (A), the (meth) acrylate (B) and the photopolymerization initiator (C) according to any one of the above (1) Composition.

(9) The resin composition for hard coating in (8) above.

(10) The composition according to the above (1) or (3), wherein (I) is the mixture (a) of (iii), the trifunctional (meth) acrylate of glycerin and the C2 to C5 aliphatic poly (Meth) acrylate compound (A).

(11) The three-component mixture (a) of (iii) (iii), the (meth) acrylate of glycerin and the C2 to C5 aliphatic poly (2-4) Of the polyisocyanate compound (b) of the formula (II) in an amount of from 0.01 to 10 equivalents of the active hydrogen group equivalent of glycerin and from 0.01 to 10 equivalents of the C2 to C5 aliphatic poly (2-4) (Meth) acrylate according to the above (1) or (10), which is reacted in an amount of 0.01 to 10 equivalents of an active hydrogen group equivalent of the (meth) acrylate and 0.1 to 50 equivalents of an isocyanate group of the polyisocyanate compound (b) (A).

(12) The pharmaceutical composition according to any one of (1) to (4), (6) or (10) above, wherein the mixture (a) (Meth) acrylate is contained in an area ratio (%) of the polymer (HPLC), and to it is added dipentaerythritol tetra (meth) acrylate and dipentaerythritol hexa ) Acrylate is 90 to 100% and the remainder is 0 to 10% is a urethane (meth) acrylate compound having an acrylate of a higher molecular weight than dipentaerythritol tri (meth) acrylate and tripentaerythritol (A).

(13) The urethane (meth) acrylate compound (A) wherein the polyisocyanate compound (b) is a diisocyanate compound alone in any one of the above (1) to (4), (6) .

(14) The polyisocyanate compound (b) is any one of the compounds (1) to (3), (5) (Meth) acrylate compound (A).

(15) A urethane (meth) acrylate compound (A) wherein the diisocyanate compound is hexamethylene diisocyanate in the above (13) or (14).

(16) The positive resist composition according to any one of (1) to (4), (6), (10) and (12) to (14), wherein the mixture (a) is dipentaerythritol tetraacrylate, dipentaerythritol Pentaacrylate and dipentaerythritol hexaacrylate, or a mixture of dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Meth) acrylate compound (A) wherein the polyisocyanate compound (b) is hexamethylene diisocyanate alone, or a combination of hexamethylene diisocyanate and hexamethylene diisocyanate trimer.

(17) A process for producing the urethane (meth) acrylate compound (A) and the photopolymerization initiator (C) described in any one of the above (1) to (4), (6), (10) .

(18) A photopolymerization initiator comprising the urethane (meth) acrylate compound (A) and the photopolymerization initiator (C) described in any one of the above (1) to (4), (6), (10) A cured film of the resin composition.

(19) In any one of (1) to (4), (6), (10) and (12) to (16), urethane (meth) acrylate having a viscosity of 60 to 40 Pa Compound (A).

By using the urethane (meth) acrylate compound (A) of the present invention, it is possible to provide a cured film having high transparency, hardness and scratch resistance and hardly generating curls or cracks, or a cured film having high transparency, And a cured film having toughness, a cured product of the resin composition, a hard coating agent comprising the resin composition, and a hard coating using the same.

Hereinafter, the present invention will be described in detail.

(Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, which are used as raw materials in the present invention, (A) (preferably a mixture of dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, (A ') containing at least two selected from the group consisting of ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, erythritol pentaacrylate and dipentaerythritol hexaacrylate} has a hydroxyl value of 80 to 120 mgKOH / g . When the hydroxyl value is within this range, the objective urethane (meth) acrylate compound (A) (preferably the urethane acrylate compound (A ')) can be obtained efficiently without causing gelation during the reaction of urethane have. From the resin composition containing the urethane (meth) acrylate compound (A) thus obtained, it is possible to obtain a hard coating having high hardness, excellent lubrication resistance and high flexibility.

In the present specification, when it is necessary to distinguish the urethane (meth) acrylate compound (A) by structure or composition, a compound containing no skeleton derived from glycerin is referred to as urethane (meth) acrylate compound (A1), a urethane (meth) acrylate compound (A2) containing a glycerin derived skeleton, a skeleton derived from glycerin, and a skeleton derived from a (meth) acrylate of a C2 to C5 aliphatic poly Is referred to as urethane (meth) acrylate compound (A3).

The dipentaerythritol poly (meth) acrylate mixture (a) (hereinafter simply referred to simply as poly (meth) acrylate mixture (a) or mixture (a)) used as the raw material is obtained by reacting dipentaerythritol (Meth) acrylic acid by dehydration condensation reaction in the presence of a dehydration condensation catalyst such as an acid catalyst to obtain (meth) acrylate of dipentaerythritol.

The mixture (a) is preferably at least one selected from the group consisting of dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa ) Acrylate, and more preferably at least three kinds selected from the group consisting of dipentaerythritol tetra, penta and hexa (meth) acrylates. Usually, the mixture (a) is a mixture of four kinds of dipentaerythritol tri, tetra, penta and hexa (meth) acrylates, or a mixture of dipentaerythritol tetra, penta and hexa (meth) It is a mixture containing species. The mixture (a) may further contain an acrylate of a tri- or higher-pentaerythritol multimer such as tripentaerythritol by-produced during the condensation reaction. Among the above (meth) acrylates of dipentaerythritol, acrylate compounds (dipentaerythritol tri, tetra, penta and hexaacrylates) are preferred over methacrylates in terms of cost and the like .

In the present invention, the content ratio of each component to the total amount of the mixture (a) is as follows in terms of area ratio (%) of high performance liquid chromatography (HPLC).

30 to 70%, preferably 30 to 60%, more preferably 35 to 55%, and still more preferably 35 (%) of dipentaerythritol penta (meth) acrylate (preferably dipentaerythritol pentaacrylate) (Meth) acrylate (preferably dipentaerythritol pentaacrylate), and further dipentaerythritol tetra and hexa (metha) acrylate (preferably dipentaerythritol pentaacrylate) are added to the dipentaerythritol penta The total amount of the triplet added with trimethylolpropane, trimethylolpropane, trimethylolpropane, trimethylolpropane, trimethylolpropane, erythritol tetra and hexaacrylate) is 85 to 100%, preferably 90 to 100%. In consideration of the by-product of the multimer in the dehydration condensation reaction, the total of the three members is 85 to 98%, preferably 90 to 97%. As the remainder, dipentaerythritol tri (meth) acrylate (preferably dipentaerythritol triacrylate) and / or acrylate of a polymeric monomer having a polymeric trimer or higher of pentaerythritol. In this case, the content of each of dipentaerythritol tetra and hexa (meth) acrylate is preferably about 1 to 40% (preferably about 10 to 30%) and about 15 to 40% , And the content of dipentaerythritol tri (meth) acrylate is about 0 to about 10%, preferably about 5% or less (including about zero). In addition, it may contain acrylates of the above-mentioned multimers.

The production method of the mixture (a) will be described in detail below.

But is not limited thereto as long as the mixture (a) used as a raw material in the present invention is obtained.

Examples of the acid catalyst used in the dehydration condensation reaction include inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid and trifluoromethanesulfonic acid, Lewis acids such as etherate, acid type ion exchange resins and the like. These acid catalysts may be used alone or in combination of two or more. Among these, preferred acid catalysts include sulfuric acid.

The amount of the acid catalyst to be used is 0.01 to 50 mol%, preferably 0.1 to 20 mol%, based on 1 mol of dipentaerythritol.

In the dehydration condensation reaction of dipentaerythritol and (meth) acrylic acid, the (meth) acrylic acid may be used in an amount of 0.1 to 20 moles, preferably 1 to 10 moles, per 1 mole 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 占 폚. However, from the viewpoint of shortening the reaction time and preventing polymerization, 75 to 120 占 폚, more preferably 100 to 120 占 폚 . ≪ / RTI >

As the reaction solvent in the dehydration condensation reaction, an azeotropic solvent capable of distilling the water generated in the reaction is preferable. As the azeotropic solvent, it is preferable that the azeotropic solvent has a boiling point of 60 to 130 캜, is azeotropic with water, and is easily separable from water.

Specifically, it is preferable to use a mixture of at least one of non-reactive organic solvents such as benzene, toluene, n-hexane, n-heptane, cyclohexane and the like. Toluene is more preferred. The amount to be used is arbitrary, but is preferably from 10 to 70 mass% with respect to the reaction mixture.

A commercially available polymerization initiator such as 4-methoxyphenol is usually added to commercially available (meth) acrylic acid, but a polymerization inhibitor may be added at the time of the reaction. Examples of such polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxytiophenol, p-benzoquinone, 2,5-dihydroxy- -Benzoquinone, phenothiazine, and the like. Cupric chloride and the like can also be used. The amount used is 0.01-1 mass% with respect to the reaction mixture.

The urethane (meth) acrylate compound (A)

(I) a polyisocyanate compound (b) comprising a diisocyanate compound (i), (ii) or (iii) Can:

(i) a group consisting of dipentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (A) (hereinafter referred to as a mixture (a)) of dipentaerythritol poly (meth) acrylate mixture containing at least two selected and having a hydroxyl value of 80 to 120 mgKOH / g,

(ii) a mixture of the mixture (a) and glycerin,

(iii) the mixture of (a), (tri) of glycerine and (meth) acrylate of C2 to C5 aliphatic poly (2-4) alcohols.

The polyisocyanate compound (b) used in the production of the urethane (meth) acrylate compound (A) of the present invention may be any compound as long as it is a compound containing two or more isocyanate groups in one molecule. In the present invention, the diisocyanate It is essential to include a compound. As the polyisocyanate compound (b), a diisocyanate compound alone or a combination of a diisocyanate compound and another polyisocyanate is preferable. In the case of the combined use, in particular, a combination of a diisocyanate compound and a triisocyanate compound is preferable.

Examples of the polyisocyanate compound (b) usable in the present invention include aliphatic polyisocyanate compounds, aromatic polyisocyanate compounds, alicyclic polyisocyanates, their trimer or multimer compounds, buret-type polyisocyanates, Nate-type polyisocyanate, and the like. A trimer or a multimeric compound means a compound in which three isocyanate groups have formed one or more isocyanurate ring structures.

The polyisocyanate compound (b) used in the present invention may be a diisocyanate compound alone, or may be a combination of a diisocyanate compound and another polyisocyanate compound as described above. In the case of the combination of the diisocyanate compound and the other polyisocyanate compound, preferably in the case of the combination of the diisocyanate compound and the triisocyanate compound, either of them may be either one kind or a plurality of types. Normally, one kind is preferable.

Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate (1,6-hexamethylene diisocyanate), isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate , 1,3-diisocyanate cyclohexane, 1,4-diisocyanate cyclohexane, polycyclohexylmethane-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-trimethyl Cyclohexane diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate), lysine diisocyanate, Vor Nadi may be mentioned isocyanates, bicyclo heptane triisocyanate, C4~C12 aliphatic di- or triisocyanate compounds such as trimers of hexamethylene diisocyanate and the like.

Examples of the aromatic polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolylene diisocyanate, 1,4-phenylene diisocyanate, 1,6 C 1 -C 3 aromatic diisocyanate having 1 to 2 phenylene rings such as phenylene diisocyanate, 3-tetramethylxylylene diisocyanate and 4-tetramethylxylylene diisocyanate or one naphthalene ring.

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 to the other polyisocyanate compound, preferably the triisocyanate compound is 0 to 10 mol, preferably 0 to 7 mol, relative to 1 mol of the diisocyanate compound, and the other polyisocyanate compound (preferably triisocyanate compound) More preferably 0 to 5 moles, and still more preferably 0 to 3 moles.

Among the diisocyanate compounds, aliphatic diisocyanates are preferable, and C4-C12 aliphatic diisocyanates are particularly preferable. Hexamethylene diisocyanate is most preferable, and among the triisocyanate compounds, hexamethylene diisocyanate trimer is preferable.

The ratio of the polyisocyanate compound (b) to the mixture (a) is preferably such that the amount of the polyisocyanate compound (b) added to the mixture (a) (the dipentaerythritol poly (meth) acrylate mixture Is usually in the range of 0.1 to 50 equivalents, and preferably in the range of 0.1 to 10 equivalents. When glycerin is reacted, glycerin is usually used in an amount of 0.01 to 10 equivalents, preferably 0.1 to 1 equivalent, of the active hydrogen group equivalent per 1 equivalent of the active hydrogen group in the poly (meth) acrylate mixture (a) Range.

The active hydrogen group in the mixture (a) means a hydrogen atom in the hydroxyl group. The active hydrogen group in the (meth) acrylate of glycerin and the C2 to C5 aliphatic poly (2-4) Quot; means a hydrogen atom in the hydroxyl group in the hydroxyl group. In this specification, the term hydroxyl equivalent is also used, but it is used in the same sense as the active hydrogen group equivalent.

The proportion of the polyisocyanate compound (b) relative to 1 mole of the mixture (a) is such that the hydroxyl equivalent of the mixture (a) and the isocyanate group equivalent of the polyisocyanate compound (b) and the glycerin and C2 to C5 aliphatic poly (B) is used in an amount of about 0.3 to 1 mole relative to 1 mole of the mixture (a), and the amount of the polyisocyanate compound (b) Preferably about 0.3 to about 0.9 mole, and more preferably about 0.33 to about 0.8 mole.

For example, when the component (I) is a mixture (a) of the component (i) alone, the amount of the polyisocyanate compound (b) is preferably about 0.3 mol to 0.7 mol, About 0.33 mol to about 0.6 mol.

When the component (I) is (ii) or (iii) (when the mixture (a) is used in combination with glycerin), the amount of the polyisocyanate compound (b) Is increased. The amount of the polyisocyanate compound (b) which is increased is preferably in the range of about one half to one half of the number of moles of glycerin used. For example, when glycerin is used in a proportion of about 0 to about 0.3 mol, preferably about 0 to about 0.2 mol, per mol of the mixture (a), the amount of the polyisocyanate compound (b) (preferably, diisocyanate Compound, or a combination of a diisocyanate compound and a triisocyanate compound) is in the range of about 0 to about 0.3 mol, and more preferably about 0 to about 0.2 mol, per mol of the mixture (a). When the (meth) acrylate of the C2-C5 aliphatic poly (2-4) ol has a hydroxyl group, it is preferable to increase the polyisocyanate compound (b) so that the equivalent number of NCO corresponding to the equivalent number of the hydroxyl groups is obtained. Usually, the number of equivalents of NCO of the polyisocyanate compound (b) to be reacted and the total number of equivalents of the active hydrogen groups of each component in the mixture (a) . ≪ / RTI >

In this specification, 1 mole of the mixture (a) is added to the ratio (mole number) of each component in the mixture (a) to the total amount of the mixture (a) And the sum of the values calculated by multiplying the respective molecular weights is defined as the molecular weight of the mixture (a).

Examples of the (meth) acrylate of the C2-C5 aliphatic poly (2-4) used in (iii) of (I) include C2-C5 aliphatic poly (2-4) such as ethylene glycol, propylene glycol, pentaerythritol, (Meth) acrylate obtained by the reaction of an (meth) acrylic acid with an olefin. As the (meth) acrylate, it is preferable to contain 30 to 100 mass%, preferably 50 to 100 mass% of the (meth) acrylate having a hydroxyl group with respect to the total amount of the (meth) acrylate Acrylates of C2-C5 aliphatic poly (2-4) alcohols having no hydroxyl groups. (Meth) acrylate of pentaerythritol (preferably pentaerythritol di or tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, preferably pentaerythritol tetra More 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 1: 0.6).

The reaction between the component (I) containing the mixture (a) and the polyisocyanate (b) of (II) can be carried out in the same manner as in the usual urethanization reaction. The reaction can be carried out, if necessary, in the presence of a ketone solvent such as an inert organic solvent, for example, butanone, and a catalyst.

The reaction temperature is usually in the range of 30 to 150 占 폚, preferably 50 to 100 占 폚. The end point of the reaction is determined by reacting the residual isocyanate group (NCO) content with an excess of n-butylamine, and determining by reversing the reaction with 1N hydrochloric acid. The residual isocyanate group (NCO) content of the polyisocyanate (b) Is less than or equal to 0.5%, preferably less than or equal to 0.1% with respect to the isocyanate group (NCO) content.

A catalyst may be added for the purpose of shortening the reaction time. As this catalyst, any one of a basic catalyst and an acid catalyst can be used.

Examples of the basic catalyst include pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, amines such as ammonia, and phosphines such as tributylphosphine and triphenylphosphine.

Examples of the acidic catalyst include metal alkoxides such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, titanium tetrabutoxide and zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2- Ethylhexanoate tin, octyltin tris laurate, dibutyl tin dilaurate, octyl tin diacetate, and the like. Acidic catalysts of tin compounds are preferred, with dibutyltin dilaurate being more preferred.

The addition amount of these catalysts is usually 0.1 part by mass or more and 1 part by mass or less based on 100 parts by mass of the polyisocyanate compound (b).

In the reaction, in order to prevent polymerization during the reaction, a polymerization inhibitor (for example, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, Quinone, 2,5-dihydroxy-p-benzoquinone, phenothiazine, etc.) is preferably used. The amount of the polymerization inhibitor to be used is 0.01% by mass or more and 1% Is not less than 0.05% by mass and not more than 0,5% by mass.

The urethane (meth) acrylate compound (A) obtained as described above is not a single urethane compound but is obtained as a mixture of urethane compounds having different degrees of polymerization and the like, like a polymer compound and the like. Particularly, when the poly (meth) acrylate mixture (a) is reacted with the polyisocyanate compound (b) in the presence of glycerin or a (meth) acrylate of a C2 to C5 aliphatic poly (2-4) Is a mixture of complex condensation polymers (urethane (meth) acrylate compound).

The viscosity (60 캜) of the resultant urethane (meth) acrylate compound (A) is about 5 to 40 Pa · s, preferably about 10 to 38 Pa · s, more preferably about 12 to 38 Pa · s, Is about 14 to 35 Pa · s. Also among the most preferable ones, when the viscosity is 15 Pa · s or more, the curl is less, and when the viscosity is 17 Pa · s or more, the curl is less, and when the viscosity is 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 about 5,000 to 35,000. In order to obtain a cured film having 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 1,500 to 2,300, more preferably 1,600 to 2,300, further preferably 1,700 to 2,300, and most preferably 1,700 to 2,100.

One of the more preferred forms of the urethane (meth) acrylate compound (A) has a weight average molecular weight of about 4,500 to 35,000, a number average molecular weight of 1,500 to 2,300, and a viscosity (60 ° C) of 5 to 40 Pa · s. One of the more preferred forms is that 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.

The urethane (meth) acrylate compound of the present invention is a copolymer obtained by copolymerizing urethane (meth) acrylate (urethane (meth) acrylate) in an amount of 60 To about 90%, preferably about 60 to 85%, and the balance of about 10 to 40%, preferably about 15 to 40%, of the unreacted (meth) acrylate Pentaerythritol hexa (meth) acrylate, and non-urethane-modified pentaerythritol oligomers (oligomers of tri or higher)).

(Meth) acrylate mixture (a) with the bifunctional polyisocyanate compound (b) (diisocyanate compound) and the polyfunctional polyisocyanate compound (b) without coexistence of the (meth) In the reaction, the urethane (meth) acrylate compound (A1) of the following formula (1) is obtained.

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

(1) In the case of Y, X is an isocyanate residue, a and b and c are positive integers and 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 terminal, c is 0, X is an isocyanate residue, a and b are integers of 1? A? 5, 0? B? 4, b = 5,

(3) When B is present at a terminal other than the terminal, c is 0, X is an isocyanate residue, a and b are integers of 1? A? 4, 0 b? 3, and a + b = 4. In the case where B is present at a terminal other than the terminal, in theory, B may represent Y independently of Y, but in the present specification, for the sake of simplicity, it is expressed as described above.

(2) is a divalent group, and when A and B are present at the terminal, independently of the case of Y and when B is present at the terminal other than the terminal, Is a monovalent group.

In the case of (2) (when A is present or when B is present at the end), the formula (2) can be represented by the following formula (2a).

In the above 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 a urethane (meth) acrylate compound (A) of the present invention and a photopolymerization initiator (C), and suitably contains a (meth) acrylate (B) and a curing accelerator ), Diluent (E), and other ingredients.

Examples of the other components include a leveling agent, a defoaming agent, an ultraviolet absorber, a photostabilizer, 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.

The resin composition of the present invention preferably contains an organic solvent as a diluent (E) so that it can be easily formed into a film 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, By mass, more preferably about 50% by mass to about 95% by mass, and even more preferably about 70% by mass to about 95% by mass.

The content of the urethane (meth) acrylate compound (A) relative to the total amount of the resin composition of the present invention is usually from 5 to 97 mass%, preferably from 20 to 95 mass%, and more preferably from 40 to 95 Mass%, and more preferably about 45 to 95%.

Examples of the (meth) acrylate (B) 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 more (meth) acrylate: acryloyl group having two or three Acrylate) or the like. (Meth) acrylate oligomer (except for the urethane (meth) acrylate compound (A)), a polyester (meth) acrylate oligomer or an epoxy (Meth) acrylate oligomer and the like. These may be used alone or in combination of two or more.

In the present invention, a poly (meth) acrylate compound having 2 to 6 (meth) acryloyl groups is preferable. Preferred examples of the poly (meth) acrylate compound include C1 to C12 aliphatic glycol di (meth) acrylate or dipentaerythritol poly (3-6) (meth) acrylate, and more preferably C1 to C12 aliphatic glycols Diacrylate or dipentaerythritol poly (3-6) acrylate.

The C1-C12 aliphatic glycol diacrylate is preferably a C1-C6 aliphatic glycol diacrylate.

When a film having flexibility is desired, C1-C12 aliphatic glycol diacrylate is preferable, and when a cured product having high hardness is desired, dipentaerythritol poly (3-6) acrylate is preferable.

In the present invention, the expression " (meth) acrylate " For example, in the case of "(meth) acrylate", it is used in the meaning of acrylate or methacrylate. The expression "poly (3-6)" or "poly (2-4)" means that "poly" is "3-6" or "2-4" or the like.

As the mono (meth) acrylate, for example, acryloylmorpholine; (Meth) acrylate such as 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylate such as phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like; Ethyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, phenylthioethyl (meth) acrylate, 2-hydroxy- (Meth) acrylate such as methoxy (meth) acrylate, and phenylphenol epoxy (meth) acrylate.

Examples of the bifunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane di (Meth) acrylate, bisphenol A (poly) ethoxydi (meth) acrylate, bisphenol A (poly) propoxydi (meth) acrylate, bisphenol F (Meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of (poly) ethylene glycol di (meth) acrylate hydroxypivalic acid neopentyl glycol (for example, Nippon Kayaku Co., Ltd.) KAYARAD HX-220, HX-620, etc.) and epoxy acrylates such as bisphenol A diepoxyacrylate.

Examples of the trifunctional or higher polyfunctional (meth) acrylate include ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolooctane tri (meth) acrylate, trimethylolpropane Poly (meth) acrylates such as methylol such as trimethylolpropane tri (meth) acrylate, trimethylol propane (poly) propoxy tri (meth) acrylate and trimethylol propane (poly) ethoxy (poly) propoxy tri (meth) Acrylate; Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol (poly) ethoxy tetra (meth) acrylate, pentaerythritol (poly) propoxytetra (meth) Poly (meth) acrylates of erythritol such as tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Poly (meth) acrylate isocyanurates such as tris [(meth) acryloyloxyethyl] isocyanurate and caprolactone modified tris [(meth) acryloyloxyethyl] isocyanurate; .

(Poly) ester (meth) acrylate include di (meth) acrylate of (poly) ester diol and the like.

The (poly) ester diol can be obtained by the 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 and (poly) Butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, Diethyl-1,5-pentanediol, and 2-butyl-2-ethyl-1,3-propanediol; Alicyclic alkyldiols such as cyclohexane-1,4-dimethanol; Bisphenol A (poly) ethoxydiol, or bisphenol A (poly) propoxydiol.

Examples of the dibasic acid or its anhydride include succinic acid, adipic acid, azelaic acid, dimeric 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 the reaction product of a diol compound (including the polyester diol) and an organic polyisocyanate (Except for the urethane (meth) acrylate compound (A)).

Examples of the diol compound include (poly) ethylene glycol (e.g., ethylene glycol, diethylene glycol, triethylene glycol, or a polyethylene glycol having a higher degree of polymerization), (poly) propylene glycol (e.g., 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, Methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, C1-C12 aliphatic glycols or poly (C2-C4 alkylene) glycols such as cyclohexane-1,4-dimethanol; Bisphenol A (poly) C2-C3 alkoxydiol such as bisphenol A (poly) ethoxydiol or bisphenol A (poly) propoxydiol; A polyester diol which is a reaction product of these diol compounds with dibasic acids or anhydrides thereof; And the like. Examples of the dibasic acid or its anhydride include succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid, and anhydrides thereof.

Examples of the organic polyisocyanate used in the synthesis of the urethane (meth) acrylate oligomer include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl Chain saturated hydrocarbon isocyanates such as hexamethylene diisocyanate; Cyclic diisocyanates such as isophorone diisocyanate, norbornane diisocyanate, polycyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated toluene diisocyanate Saturated hydrocarbon isocyanate; 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4-phenylenediisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 6-isopropyl- Aromatic polyisocyanates such as diisocyanate and 1,5-naphthalene dicyanate; And the like.

Examples of the (poly) ester (meth) acrylate oligomer include (poly) ester (meth) acrylate oligomers obtained by the reaction of the above (poly) ester diol with (meth) acrylic acid.

Examples of the epoxy (meth) acrylate oligomer include an epoxy (meth) acrylate oligomer obtained by reaction of an epoxy resin with (meth) acrylic acid. 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 or more and 94% by mass or less when the solid content of the resin composition of the present invention is 100% Preferably 0 to 60% by mass, and when used, it is preferably larger than zero but preferably 5 to 60% by mass, more preferably 10 to 60% by mass. In some cases, it is preferably 20 to 80% by mass.

The content of the (meth) acrylate (B) relative to the total amount of the resin composition of the present invention is usually 0 to 50 mass%, preferably 0 to 40 mass%, more preferably 0 to 30 mass% . When used, it is preferably larger than zero, but is preferably 3 to 50 mass%, more preferably 5 to 40 mass%, and still more preferably 5 to 30 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- Acetophenones such as hexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one; Anthraquinones such as 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-chloro anthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. More specifically, in the market, a commercially available product such as Ciba Specialty Chemicals, IRGACURE ^RTM 184 (1-hydroxycyclohexyl phenyl ketone), IRGACURE 907 (2-methyl-1- (4- (methylthio) 1-one), lucylline TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) from BASF, etc. can be easily obtained. These may be used alone or in combination of two or more. Among them, 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 preferably 0.1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more when the solid content of the resin composition of the present invention is 100% 7% by mass or less.

The content of the light-polymerization 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 mass%, more preferably about 1 to 10 mass%, and even more preferably about 2 to 8 mass%.

The photopolymerization initiator (C) may be used in combination with the curing accelerator (D). Examples of the curing accelerator (D) which can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, 4-dimethylaminobenzoic acid, , Amines such as EPA, and hydrogen donors such as 2-mercaptobenzothiazole. The amount of the curing accelerator to be 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. These may be used alone or in combination of two or more.

In the resin composition of the present invention, a diluent (E) may be used if necessary. As the diluent (E), a solvent at room temperature (20 ° C) liquid, usually an organic solvent, is used. For example, lactones such as? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Heptalactone,? -Acetyl-? -Butyrolactone and? -Caprolactone; Diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Ethers such as ethylene glycol diethyl ether, tetraethylene glycol dimethyl ether and tetraethylene glycol diethyl ether; Carbonates such as ethylene carbonate and propylene carbonate; Ketones such as methyl ethyl ketone (2-butanone), methyl isobutyl ketone, cyclohexanone, and acetophenone; Phenols such as phenol, cresol and xylenol; Esters such as ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate; Hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochlorobenzene; petroleum solvents such as petroleum ether and petroleum naphtha; fluorinated alcohols such as 2H and 3H-tetrafluoropropanol; perfluorobutyl methyl ether, Hydrofluoroethers such as perfluorobutyl ethyl ether; Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-propyl alcohol; And diacetone alcohol having both of the performance of a ketone and an alcohol. These may be used alone or in combination of two or more.

Among them, an ester solvent such as ethyl acetate (preferably an acetic acid ester of a C2-3 alcohol) or a ketone (a ketone solvent) is preferable, and a C3-C6 aliphatic ketone is 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 mass%, preferably about 0 to 80 mass%, more preferably about 0 to 80 mass% About 60% by mass.

When the solid content of the resin composition of the present invention is 100 mass%, the content of the diluent (E) is about 0 to 300 mass%, preferably 0 to 200 mass%, more preferably 0 to 100 mass% 150% by mass.

In the present specification, in the content of the components of the composition, for example, the content expressed by including 0 in "0 to 90 mass%" as described above does not include the component, or is greater than 0 and 90 mass% Quot; is meant to encompass the following ranges.

The resin composition of the present invention may contain a leveling agent, a defoaming agent, an ultraviolet absorber, a photostabilizer, an antioxidant, a polymerization inhibitor, a cross-linking agent, and the like, as other additives as necessary. By including them, desired functionalities can be given respectively.

Examples of the leveling agent include a fluorine-based compound, a silicon-based compound and an acrylic compound. Examples of the ultraviolet absorber include a benzotriazole-based compound, a benzophenone-based compound and a triazine-based compound. Examples of the photostabilizer include hindered amine compounds and benzoate- Phenol-based compounds, etc. Examples of the polymerization inhibitor include methoquinone, methylhydroquinone and hydroquinone. Examples of the crosslinking agent include the above polyisocyanates and melamine compounds.

One of the preferred resin compositions of the present invention contains the urethane (meth) acrylate compound (A) of the present invention and the photopolymerization initiator (C), and further the (meth) acrylate (B) Of the resin composition.

More specifically, preferred resin compositions of the present invention are as follows. The composition ratio is a ratio with respect to 100% by mass of the solid content of the resin composition.

(i) 5 to 97% by mass of a urethane (meth) acrylate compound (A)

0.5 to 12% by mass of the photopolymerization initiator (C)

(Meth) acrylate (B) in an amount of 0 to 50 mass%, and

Wherein the diluent (E) is an organic solvent, and the organic solvent is contained in an amount of 0 to 300 mass%.

(ii) The resin composition according to the above (i), which contains 40 to 95 mass% of the urethane (meth) acrylate compound (A).

(iii) a composition containing 5 to 40% by mass of (meth) acrylate (B) or at least one of 50 to 150% by mass of an organic solvent which is a diluent (E) Resin composition.

(iv) In any one of (i) to (iii) above, the urethane (meth) acrylate compound (A) (Meth) acrylate compound (A) as described in any one of the above (5), (7) or (11) (A). ≪ / RTI >

(v) The resin composition according to any one of (i) to (iv), wherein the photopolymerization initiator (C) is a photopolymerization initiator belonging to acetophenones.

(vi) In any one of (i) to (v) above, (meth) acrylate (B) is a C1 to C12 aliphatic glycol di (meth) acrylate or dipentaerythritol poly (3-6) Acrylate.

(vii) The resin composition according to any one of (i) to (vi), wherein the diluent (E) is a ketone solvent.

The resin composition of the present invention is particularly useful as a resin composition (hard coating agent) for hard coating, and can be used as a molding material for electronic parts, electronic parts and the like to be described later.

The resin composition of the present invention can be obtained by mixing the components (A) and (C), and optionally the components (B), (D), (E) and other components in an arbitrary order .

The hard coat of the present invention can be obtained by applying the resin composition of the present invention onto a substrate, drying it if necessary, and irradiating the formed thin film with ultraviolet rays to form a cured film.

More specifically, the above-mentioned resin composition is applied to a substrate having a thickness of 0.1 占 퐉 or more and 300 占 퐉 or less, usually 0.1 占 퐉 or more and 50 占 퐉 or less, more preferably 1 占 퐉 or more Or less and 20 탆 or less, and if necessary, drying and then irradiating 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 탆 to 300 탆, preferably about 1 탆 to 250 탆. When a coating film is formed on a base film, the film thickness after curing is usually from 0.1 to 50 μm, preferably from 1 to 20 μm, more preferably to 10 μm or less, further preferably to 7 μm or less desirable.

Examples of the base film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetylcellulose, polyethersulfone, and cycloolefin-based polymers. The film to be used may be a pattern, an adhesive layer, a surface treatment such as a corona treatment, or a release treatment.

Examples of the application method of the resin composition include a bar coater coating, a Meyer bar coating, an air knife coating, a gravure coating, a reverse gravure coating, a microgravure coating, a micro reverse gravure coating, a die coater coating, Coating, spray coating, and the like.

For curing, ultraviolet rays are irradiated, but an electron beam or the like may be used. In the case of curing by ultraviolet rays, an ultraviolet irradiation apparatus having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, or the like is used as a light source, and the amount of light, In the case of using a high-pressure mercury lamp, it is preferable to cure the lamp 1 having an energy of 80 to 120 W / cm 2 at a conveying speed of 5 to 60 m / min. On the other hand, in the case of curing by 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 at that time.

Since the cured coating film of the resin composition of the present invention has adhesiveness to a base material and hardness and has appropriate flexibility, it can be suitably used for display device materials. For example, a material used for a color filter used for an LCD, an EL, a rear projection display, an electronic paper, a spacer for separating a minute display element used for a PDP, an electronic paper, etc., a spacer used for an FED (SED) A solid-state image pickup device such as a digital camera, and the like. 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 image pickup device such as a digital camera. Among them, particularly, it is a color filter. This color filter has patterned colored pixels of a plurality of colors, or a black matrix and a photo-spacer made of a cured product of the photosensitive resin composition of the present invention prepared as described above.

In the present invention, the display device is a liquid crystal display device in which 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, Structure. For example, a solid-state image pickup device is manufactured by forming a color filter layer using the photosensitive resin composition of the present invention on a silicon wafer provided with a transfer electrode and a photodiode, and then laminating microlenses.

As another use of the photosensitive resin composition of the present invention, it can be used for printing ink, paint, adhesive, liquid resist ink and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise stated, in the examples, parts represent parts by mass. In the examples, abbreviations used are as follows.

DPETtriA: dipentaerythritol triacrylate

DPETtetraA: dipentaerythritol tetraacrylate

DPETpentaA: dipentaerythritol pentaacrylate

DPEThexaA: dipentaerythritol hexaacrylate, and

TPETA: acrylate of oligomers of tripentaerythritol or higher

HPLC: High performance liquid chromatography

GPC: gel permeation chromatography

The conditions for HPLC and GPC measurement are as follows.

HPLC measurement conditions

Device: SHIMADZU LC-10AD, SCL-10A, SPD-10A, CTO-10A, DGU-14A

Detector: UV 254 nm

Column: GL Science Inertsil ODS-2 (4.6 x 150 mm)

Column temperature: 40 DEG C

Eluent: acetonitrile / 0.1 wt% H ₃ PO ₄ = 60/40

Flow rate: 0.6 ml / min.

Sample injection amount: 2 μl

Sample concentration: 1 wt%

GPC measurement conditions

Device: TOSOH HLC-8220 GPC

Detector: RI

Column: TOSOH TSK-GEL SUPER HZM-N

Column temperature: 40 DEG C

Eluent: THF

Flow rate: 0.35 ml / min.

Sample injection amount: 5 μl

Sample concentration: 1 wt%

Raw material Synthetic example  One

(1.0 mol) of dipentaerythritol, 449.7 g (6.2 mol) of acrylic acid, 9.81 g of sulfuric acid, 1.03 g of cupric chloride, and 10.0 g of distilled water were charged in a reactor equipped with a reflux condenser, a stirrer, a thermometer, 424.7 g of toluene was introduced, and the reactor was heated to react for 12 hours while distilling the generated water with a solvent. After the reaction, 849.4 g of toluene was added to dilute, neutralized with 25% NaOH aqueous solution, and washed three times with 600 g of 15 mass% saline solution. 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 mgKOH / g, hydroxyl group equivalent (active hydrogen group equivalent): 701.4 g / Eq).

The proportions of DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the area ratio (%) of high performance liquid chromatography (HPLC) were 10: 43: 37: 10. The viscosity of the mixture was 6,300 mPa ((25 캜).

Raw material Synthetic example  2

(1.0 mol) of dipentaerythritol, 432.4 g (6.0 mol) of acrylic acid, 9.81 g of sulfuric acid, 0.99 g of cupric chloride, and 10.0 g of distilled water were charged in a reactor equipped with a reflux condenser, a stirrer, a thermometer, 424.7 g of toluene was introduced, and the reactor was heated to react for 12 hours while azeotropically distilling the generated supernatant with a solvent. After the reaction, 849.4 g of toluene was added to dilute, neutralized with 25% NaOH aqueous solution, and then washed three times with 600 g of 15 mass% saline solution. The solvent was distillated under reduced pressure to obtain 525.3 g of a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 92 mgKOH / g, hydroxyl equivalent: 609.9 g / Eq).

DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the area ratio (%) of HPLC was 12: 45: 36: 7. The viscosity of the mixture was 6,300 mPa 占 퐏 (25 占 폚).

Raw material Synthetic example  3

254.3 g (1.0 mol) of dipentaerythritol, 402.1 g (5.6 mol) of acrylic acid, 9.81 g of sulfuric acid, 0.92 g of cupric chloride, and 10.0 g of distilled water were charged in a reactor equipped with a reflux condenser, a stirrer, a thermometer, 424.7 g of toluene was introduced, and the reactor was heated to react for 12 hours while azeotropically distilling the generated supernatant with a solvent. After the reaction, 849.4 g of toluene was added to dilute, neutralized with 25% NaOH aqueous solution, and then washed three times with 600 g of 15 mass% saline solution. The solvent was distillated 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).

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 占 퐏 (25 占 폚).

Comparative raw materials Synthetic example  One

(1.0 mol) of dipentaerythritol, 497.2 g (6.9 mol) of acrylic acid, 9.81 g of sulfuric acid, 1.14 g of cupric chloride, and 4.8 g of triphenylphosphine were added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, 424.7 g of toluene was charged, and the reactor was heated to react for 12 hours while azeotropically distilling the generated supernatant with a solvent. After the reaction, 849.4 g of toluene was added to dilute, neutralized with 25% NaOH aqueous solution, and then washed three times with 600 g of 15 mass% saline solution. 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 mgKOH / g, hydroxyl equivalent: 1246.9 g / Eq).

DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the area ratio (%) of HPLC was 2: 30: 56: 12. The viscosity of the mixture was 6,500 mPa 占 퐏 (25 占 폚).

Comparative raw materials Synthetic example  2

(1.0 mol) of dipentaerythritol, 380.5 g (5.3 mol) of acrylic acid, 9.81 g of sulfuric acid, 0.88 g of cupric chloride, and 10.0 g of distilled water were charged in a reactor equipped with a reflux condenser, a stirrer, a thermometer, 424.7 g of toluene was charged, and the reactor was heated to react for 12 hours while azeotropically distilling the generated supernatant with a solvent. After the reaction, 849.4 g of toluene was added to dilute, neutralized with 25% NaOH aqueous solution, and then washed three times with 600 g of 15 mass% saline solution. 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).

DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA in the area ratio (%) of HPLC was 4: 30: 42: 19: 5. The viscosity of the mixture was 5,800 mPa 占 퐏 (25 占 폚).

Example  A ( Synthetic example  One)

(Hydroxyl value: 80 mgKOH / g, hydroxyl equivalent: 701.4 g / Eq) of the DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the starting material Synthesis Example 1 were added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, (0.64 mole) as a polymerization inhibitor, 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanation catalyst were added and stirred until homogeneous, and the internal temperature was adjusted to 50 캜. Subsequently, 53.53 g (0.32 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 DEG C, and the mixture was reacted at 80 DEG C for 6 hours. When the above-mentioned NCO content became 0.1% or less, To obtain the urethane acrylate of the present invention.

This had an average molecular weight (Mw = 4,500, Mn = 1,500) and a viscosity of 6 Pa · s (60 ° C).

As to the obtained urethane acrylate, the components were confirmed by HPLC and GPC. As a result, it was found that the content of urethane acrylate was 64% (ratio with respect to the total amount) and that the urethane acrylate (unreacted DPEThexaA and by- Acrylate of pentaerythritol oligomer) was 36%.

Example  B ( Synthetic example  2)

(A hydroxyl value: 92 mg KOH / g, a hydroxyl equivalent: 609.9 g / Eq) of the DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the raw material synthesis example 2 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, (0.72 mole) as a polymerization inhibitor, 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanation catalyst were added and stirred until homogeneous, and the internal temperature was adjusted to 50 캜. Subsequently, 60.59 g (0.36 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 DEG C, and the mixture was reacted at 80 DEG C for 6 hours. When the above-mentioned NCO content became 0.1% or less, To obtain urethane acrylate.

This was an average molecular weight (Mw = 5,500, Mn = 1,800) and a viscosity of 11 Pa · s (60 ° C).

The urethane acrylate thus obtained had a urethane acrylate content of 74% (ratio with respect to the total amount) and a non-urethane acrylate content of 26%.

Example  C ( Synthetic example  3)

DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 120 mgKOH / g, hydroxyl equivalent: 467.6 g / Eq) obtained in Synthesis Example 3 were added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, , 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanation catalyst were added and stirred until homogeneous, and the internal temperature was adjusted to 50 캜. Subsequently, 76.22 g (0.45 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 DEG C, and the mixture was reacted at 80 DEG C for 6 hours. When the aforementioned NCO content became 0.1% or less, To obtain urethane acrylate.

This had an average molecular weight (Mw = 7,800, Mn = 1,700) and a viscosity of 16Pa 占 퐏 (60 占 폚).

The obtained urethane acrylate had a urethane acrylate content of 73% (a ratio to the total amount) and a non-urethane acrylate content of 27%.

Example  D ( Synthetic example  4)

(Hydroxyl value: 92 mgKOH / g, hydroxyl equivalent: 609.9 g / Eq) of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the raw material synthesis example 2 were added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, (0.04 mol) of glycerin, 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 were added and homogeneously mixed And the internal temperature was set to 50 캜. Subsequently, 55.83 g (0.33 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 DEG C, and the mixture was reacted at 80 DEG C for 6 hours. When the above-mentioned NCO content became 0.1% or less, Respectively. The mixture was heated to 60 占 폚 and the solvent (2-butanone) was distilled under reduced pressure to obtain the urethane acrylate of the present invention.

This had an average molecular weight (Mw = 10,300, Mn = 1,800) and a viscosity of 18 Pa · s (60 ° C).

The urethane acrylate thus obtained had a urethane acrylate content of 74% (ratio with respect to the total amount) and a non-urethane acrylate content of 26%.

Example  E ( Synthetic example  5)

(Hydroxyl value: 92 mgKOH / g, hydroxyl equivalent: 609.9 g / Eq) of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the raw material synthesis example 2 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, (0.05 mole) of glycerin, 0.50 mole of pentaerythritol tetraacrylate and 29.06 g (07 mole) of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (weight parts mixing ratio: 70/30, hydroxyl group equivalent: 421.9 g / Butanone as a polymerization inhibitor, 0.20 g of 4-methoxyphenol as a polymerization inhibitor and 0.20 g of dibutyltin dilaurate as a urethanation catalyst were added and stirred until homogeneous, and the internal temperature was adjusted to 50 캜. Subsequently, 57.93 g (0.34 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 DEG C, and the mixture was reacted at 80 DEG C for 6 hours. When the above-mentioned NCO content became 0.1% or less, Respectively. The mixture was heated to 60 占 폚 and the solvent (2-butanone) was distilled under reduced pressure to obtain the urethane acrylate of the present invention.

This had an average molecular weight (Mw = 11,300, Mn = 1,700) and a viscosity of 17Pa 占 퐏 (60 占 폚).

The content of urethane acrylate in the obtained urethane acrylate was 74% (ratio with respect to the total amount), and the content of urethane acrylate was 26%.

Example  F ( Synthetic example  6)

A mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 92 mgKOH / g, hydroxyl equivalent: 609.9 g / Eq) obtained in the starting material Synthesis Example 2 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, (0.07 mole) of 2-hydroxyethyl acrylate, 4.46 g (0.05 mole) of glycerin, 100.00 g of 2-butanone, 0.20 g of 4-methoxyphenol as a polymerization inhibitor, , 0.20 g of dibutyltin dilaurate was added and stirred until homogeneous, and the internal temperature was set to 50 캜. Subsequently, 61.15 g (0.36 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 DEG C, and the mixture was reacted at 80 DEG C for 6 hours. When the aforementioned NCO content became 0.1% or less, Respectively. The mixture was heated to 60 占 폚 and the solvent (2-butanone) was distilled under reduced pressure to obtain the urethane acrylate of the present invention.

This had an average molecular weight (Mw = 9,500, Mn = 1,800) and a viscosity of 17 Pa · s (60 ° C).

The urethane acrylate thus obtained had a urethane acrylate content of 74% (ratio with respect to the total amount) and a non-urethane acrylate content of 26%.

Example  G ( Synthetic example  7)

(Hydroxyl value: 92 mg KOH / g, hydroxyl equivalent: 609.9 g / Eq) (obtained in Synthesis Example 2 of Raw Material Synthesis 2) in DPT (0.08 mole) of 2-hydroxyethyl acrylate, 5.91 g (0.06 mole) of glycerin, 100.00 g of 2-butanone, 0.20 g of 4-methoxyphenol as a polymerization inhibitor, , 0.20 g of dibutyltin dilaurate was added and stirred until homogeneous, and the internal temperature was set to 50 캜. Subsequently, 64.73 g (0.38 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 DEG C, and the mixture was reacted at 80 DEG C for 6 hours. When the aforementioned NCO content became 0.1% or less, Respectively. The mixture was heated to 60 占 폚 and the solvent (2-butanone) was distilled under reduced pressure to obtain the urethane acrylate of the present invention.

This had an average molecular weight (Mw = 19,700, Mn = 1,800) and a viscosity of 27 Pa 占 퐏 (60 占 폚).

The urethane acrylate thus obtained had a urethane acrylate content of 75% (a ratio to the total amount) and a non-urethane acrylate content of 25%.

Example  H ( Synthetic example  8)

(A hydroxyl value: 92 mgKOH / g, a hydroxyl equivalent: 609.9 g / Eq) of the DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the starting material Synthesis Example 2 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, (0.54 mol) 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 were added and stirred until homogeneous, 50 < 0 > 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 DEG C, And the point of time when the above-mentioned NCO content became 0.1% or less was regarded as the end point of the reaction. The mixture was heated to 60 占 폚 and the solvent (2-butanone) was distilled under reduced pressure to obtain the urethane acrylate of the present invention.

This had an average molecular weight (Mw = 16,300, Mn = 2,000) and a viscosity of 24 Pa 占 퐏 (60 占 폚).

The urethane acrylate thus obtained had a urethane acrylate content of 74% (ratio with respect to the total amount) and a non-urethane acrylate content of 26%.

Example  I ( Synthetic example  9)

(Hydroxyl value: 92 mgKOH / g, hydroxyl equivalent: 609.9 g / Eq) of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the raw material synthesis example 2 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, (0.55 mol) of 2-butanone, 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 urethanation catalyst were added and stirred until homogeneous, 50 < 0 > 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 DEG C, And the point of time when the above-mentioned NCO content became 0.1% or less was regarded as the end point of the reaction. The mixture was heated to 60 占 폚 and the solvent (2-butanone) was distilled under reduced pressure to obtain the urethane acrylate of the present invention.

This had an average molecular weight (Mw = 8,500, Mn = 1,800) and a viscosity of 12 Pa 占 퐏 (60 占 폚).

The urethane acrylate thus obtained had a urethane acrylate content of 74% (ratio with respect to the total amount) and a non-urethane acrylate content of 26%.

Example  J ( Synthetic example  10)

(Hydroxyl value: 80 mgKOH / g, hydroxyl equivalent: 701.4 g / Eq) of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the starting material Synthesis Example 1 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, (0.54 mol) 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 were added and stirred until homogeneous, 50 < 0 > 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., and the mixture was reacted at 80 ° C. for 6 hours And the point of time when the above-mentioned NCO content became 0.1% or less was regarded as the end point of the reaction. The mixture was heated to 60 占 폚 and the solvent (2-butanone) was distilled under reduced pressure to obtain the urethane acrylate of the present invention.

This had an average molecular weight (Mw = 11,700, Mn = 1,800) and a viscosity of 23 Pa · s (60 ° C).

The obtained urethane acrylate had a urethane acrylate content of 66% (a ratio to the total amount) and a non-urethane acrylate content of 34%.

Example K (Synthesis Example 11)

(Hydroxyl value: 120 mgKOH / g, hydroxyl equivalent: 467.6 g / Eq) of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the starting material Synthesis Example 3 was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, (0.50 mol) 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 were added and stirred until homogeneous, 50 < 0 > 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 DEG C, And the point of time when the above-mentioned NCO content became 0.1% or less was regarded as the end point of the reaction. The mixture was heated to 60 占 폚 and the solvent (2-butanone) was distilled under reduced pressure to obtain the urethane acrylate of the present invention.

This had an average molecular weight (Mw = 27,700, Mn = 2,000) and a viscosity of 32 Pa 占 퐏 (60 占 폚).

The urethane acrylate thus obtained had a urethane acrylate content of 74% (ratio with respect to the total amount) and a non-urethane acrylate content of 26%.

compare Synthetic example  One

A DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 45 mgKOH / g, hydroxyl equivalent weight: 1246.9 g / Eq) obtained in the comparative raw material Synthesis Example 1 were added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanation catalyst were added and stirred until homogeneous, and the internal temperature was adjusted to 50 캜. Subsequently, 26.61 g (0.16 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 DEG C, and the mixture was reacted at 80 DEG C for 6 hours. When the above-mentioned NCO content became 0.1% or less, To obtain urethane acrylate.

This had 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% (a ratio to the total amount) and a non-urethane acrylate content of 52%.

compare Synthetic example  2

A mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 140 mgKOH / g, hydroxyl equivalent: 400.8 g / mol) obtained in Comparative Synthesis Example 2 was added to a reactor equipped with a stirrer, a reflux condenser, Eq), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanation catalyst were added and stirred until homogeneous, and the internal temperature was adjusted to 50 캜 Respectively. Subsequently, 86.72 g (0.52 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 DEG C, and the mixture was reacted at 80 DEG C for 2 hours to cause gelation, and the desired urethane acrylate was not obtained.

compare Synthetic example  3

(Hydroxyl value: 92 mgKOH / g, hydroxyl equivalent: 609.9 g / Eq) of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in the raw material synthesis example 2 were added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanation catalyst were added and stirred until homogeneous, and the internal temperature was adjusted to 50 캜. 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 DEG C, and the mixture was reacted at 80 DEG C for 4 hours to cause gelation, Acrylate was not obtained.

compare Synthetic example  4

DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 120 mgKOH / g, hydroxyl equivalent: 467.6 g / Eq) obtained in Synthesis Example 3 were added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanation catalyst were added and stirred until homogeneous, and the internal temperature was adjusted to 50 캜. 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 DEG C, and the mixture was reacted at 80 DEG C for 2 hours to cause gelation, Acrylate was not obtained.

Example  1-4 and Comparative Example  1-2

Each component was mixed with the composition shown in Table 1 and mixed until uniform, to prepare the resin composition of the present invention and the resin composition of the comparative example. Each of the obtained resin compositions was coated on a PET film (thickness: 125 mu m) which had been subjected to the easy adhesion treatment with a bar coater and dried at about 80 to 100 DEG C. [ Each obtained coating film was irradiated with ultraviolet rays by an ultraviolet ray irradiator (JAPAN STORAGE BATTERY CO, LTD .: CS30L-1-1) to cure the coating film. To obtain a PET film (hard coating film) having a hard coat of about 5 mu m in film thickness.

The curing conditions are as follows.

Curing conditions; (Irradiation energy: about 300 mW / cm 2, about 200 mJ / cm 2), a high pressure mercury lamp 120 W / cm, a lamp height 10 cm, and a conveyor speed 10 m /

The units of numerical values in Table 1 represent " mass parts ".

* 1, DPHA: dipentaerythritol pentaacrylate / hexaacrylate mixture

* 2, MEK: methyl ethyl ketone

* 3, Irg.184: 1-hydroxycyclohexyl phenyl ketone from Ciba Specialty Chemicals,

The following items were evaluated only for the hard coating film obtained in Examples 1 to 4 and Comparative Examples 1 to 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, a pencil was rubbed with a pencil at an angle of 45 degrees from the top by applying a load of 750 g from the top to a polyester film having a cured coating film to be measured, and the hardness of the pencil was found to be not damaged more than four times in five times .

(Adhesion)

The surface of the hard coat film obtained after the light resistance test was damaged with a cross (one side of 30 mm) with a cutter, a cellophane tape was attached thereon, and peeled at an angle of 90 degrees.

○: No peeling

×: Peeling occurred

(Scratch resistance)

A load of 200 g / cm < 2 > was applied to Steel Wool # 0000, and the surface of the obtained hard coat film was made to reciprocate 10 times, and the damaged state was visually confirmed.

○: No damage

X: Damage occurred

(curl)

The obtained hard coat film was cut into 5 cm x 5 cm, left in a drying furnace at 80 ° C for 1 hour, and returned to room temperature. The height of each of the four sides rising from the horizontal stand was measured, and the sum of the four sides was taken as the measured value (unit: mm). At this time, the curl of the substrate itself was 0 mm.

(Exterior)

Cracks, whitening, cloudiness, etc. of the surface were visually judged.

evaluation

○: Good

X: Significant cracks

As clearly shown from the results in Table 2, in the film having the cured coating obtained by curing the resin composition of the present invention, the hardness, the adhesion and the scratch resistance were good and cracks were not generated, Is small.

Example  5 to 7 and Comparative Example  3

Each component was blended with the composition shown in Table 3 and mixed until uniform, to prepare the resin composition of the present invention and the resin composition of the comparative example. Each of the obtained resin compositions was coated on a stainless steel plate with a bar coater. Each obtained coating film was irradiated with ultraviolet rays by an ultraviolet ray irradiator (Japan Battery Co., Ltd.) in a nitrogen atmosphere to cure the coating film.

The thickness of each of the obtained cured films was about 200 mu m. This cured film was peeled off from the stainless steel plate to obtain a test cured film.

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).

The numerical values in Table 3 indicate " mass parts ".

* 4, HDDA: 1,6-hexanediol diacrylate

(Tensile test)

Dumbbell-shaped test pieces were prepared from the films obtained in Examples 5 to 7 and Comparative Example 3 according to JIS K 7162, and the following data were measured using a tensile tester. The evaluation results are shown in Table 4.

1: Young's modulus (modulus of elasticity)

2: Breaking point stress

3: breaking point

As is clear from the results in Table 4, it can be seen that the cured coating obtained by curing the resin composition of the present invention has a large breaking point stress and a breaking point elongation, which is more flexible and tough than the comparative example.

Example  8-15

The components shown in the following Table 5 were mixed and mixed until uniform, to prepare the resin composition of the present invention. In the table, " MEK " and " Irg.184 "

Using each of the obtained resin compositions, a PET film (hard coating film) having a hard coat thickness of about 5 탆 was obtained in the same manner as in Examples 1 to 4 above.

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 clearly shown from the results of Table 6, in the film having the cured coating obtained by curing the resin composition of the present invention, the hardness, adhesiveness, and scratch resistance are good and cracks are not generated.

The cured coating obtained by curing the resin composition of the present invention is excellent in hardness, adhesion, and scratch resistance, and has a small curl, flexibility, and strong characteristics such as no cracking, It has a feature that it has.

(Industrial availability)

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 favorable as a material for a plastic film, a hard coating of a small chassis, a color filter, a black matrix, and a spacer.

Claims (19)

(I) A urethane (meth) acrylate compound (A) obtained by reacting any one of the following (i), (ii) or (iii) with a polyisocyanate compound (b) containing a diisocyanate compound And urethane acrylate compositions comprising non-urethane acrylate compositions:
(i) a group consisting of dipentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (A) (hereinafter referred to as a mixture (a)) of dipentaerythritol poly (meth) acrylate having at least two selected and having a hydroxyl value of 80 to 120 mgKOH / g,
(ii) a mixture of the mixture (a) and glycerin,
(iii) the mixture of (a), (tri) of glycerine and (meth) acrylate of C2 to C5 aliphatic poly (2-4) alcohols. The urethane acrylate composition of claim 1, wherein (I) is the mixture (a) of (i). The polyisocyanate compound (b) of claim 1, wherein the polyisocyanate compound (b) 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 mole of the diisocyanate compound Wherein the triisocyanate compound is in a proportion of 0 to 10 moles. The urethane acrylate composition according to claim 1, wherein the urethane (meth) acrylate compound (A) is represented by the following formula (1):

In this formula,
X is an isocyanate residue,
n is an integer of 0 to 100,
Y is an organic group represented by the following formula (2): wherein a, b and c are integers of 1? A? 4, 0 b? 3 and 0? C? 3, 4),
A is an organic group represented by the following formula (2)

ego
X is an isocyanate residue, c is 0, a and b are integers of 1? A? 5, 0 b? 4, and a + b = 5,
B is an organic group of the above formula (2) (wherein X is an isocyanate residue, c is 0,
(i) when B is present at the terminal, an integer of 1? a? 5, 0? b? 4, and a + b = 5,
(ii) When B is present at a terminal other than the terminal, a and b in the above formula are integers of 1? a? 4, 0 b? 3, and a + b = 4. (A) and the polyisocyanate compound (b) of the mixture (a) and the mixture (a) of the polyisocyanate compound (b) To 50 equivalents based on the total weight of the urethane acrylate composition. The urethane acrylate composition according to claim 1, wherein (I) is the mixture (a) of (ii) and glycerin. (A), the glycerin and the polyisocyanate compound (b) of the first claim (II) in an amount of from 0.01 to 10 equivalents of an active hydrogen group in glycerol per equivalent of the active hydrogen group in the mixture (a) In an equivalent amount of an equivalent of an isocyanate group in the polyisocyanate compound (b) of the formula (II). A resin composition comprising the urethane acrylate composition, (meth) acrylate (B), and the photopolymerization initiator (C) according to claim 1. The resin composition according to claim 8, which is used for hard coating. The urethane acrylate composition of claim 1, wherein (I) is the triad of (a) the mixture of (iii), the (meth) acrylates of glycerin and C2 to C5 aliphatic poly (2-4) alcohols. The mixture of (a) the glycerin and the (meth) acrylate of the C2 to C5 aliphatic poly (2-4) and the triisocyanate of the polyisocyanate of the above (II) The compound (b) is used in an amount of 0.01 to 10 equivalents of the active hydrogen group of glycerin and 1 to 10 equivalents of the (meth) acrylate of the C2 to C5 aliphatic poly (2-4) The equivalent of 0.01 to 10 equivalents of a hydrogen group, and the equivalent of an isocyanate group of a polyisocyanate compound (b) of 0.1 to 50 equivalents. The method according to claim 1, wherein the mixture (a) of the mixture (a) is a mixture of a mixture of (a) (Meth) acrylate is contained in an amount of 90 to 100%, and the remainder 0 (meth) acrylate is contained in an amount of 35 to 60%, and the sum of the triplet of dipentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (Meth) acrylate of dipentaerythritol tri (meth) acrylate and dipentaerythritol or higher is (meth) acrylate. The urethane acrylate composition according to claim 1 or 12, wherein the polyisocyanate compound (b) is a diisocyanate compound alone. The urethane acrylate composition according to claim 1 or 12, wherein the polyisocyanate compound (b) is a combination of a diisocyanate compound and a triisocyanate compound. 14. The urethane acrylate composition of claim 13, wherein the diisocyanate compound is hexamethylene diisocyanate. The composition according to claim 1, wherein the mixture (a) is a mixture of triplets of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, or a mixture of dipentaerythritol triacrylate, Dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, and the polyisocyanate compound (b) is a mixture of hexamethylene diisocyanate alone or a mixture of hexamethylene diisocyanate and hexamethylene A urethane acrylate composition which is both a diisocyanate trimer. A resin composition comprising the urethane acrylate composition according to claim 1 and a photopolymerization initiator (C). A cured film of a resin composition containing the urethane acrylate composition according to claim 1 and a photopolymerization initiator (C). The urethane acrylate composition according to claim 1, having a viscosity (60 캜) of 5 to 40 Pa · s.