CN102803332B - Urethane (meth) acrylate compound and resin composition containing same - Google Patents

Abstract

This invention provides a urethane (metha) acrylate compound (A), a resin composition containing the urethane (metha) acrylate compound (A) and a photo-polymerizing initiator (C), a cured article of the resin composition, a hard coating agent and a hard coating. The hard coating film obtained by curing the resin composition has excellent handness, ahesion, strength against scratch, and such properties of avoiding curlings and crackings. The urethane (metha) acrylate compound (A) is obtained by reacting the following (I) with (II), wherein (I) is any one of the following (i), (ii), or (iii): (i) dipentaerythritol poly (metha) acrylate (a) mixture having a hydroxyl value of 80 to 120 mg KOH/g (hereinafter referred to as mixture (a)), the mixture (a) containing at least 2 of the compounds selected from the group consisting of dipentaerythritol tri (metha) acrylate, dipentaerythritol tetra (metha) acrylate, dipentaerythritol penta (metha) acrylate, and dipentaerythtol hexa (metha) acrylate, (ii) both of the mixture (a) and a glycerin; or (iii) all three of the mixture (a), the glycerin and a (metha) acrylate of C2 to C5 aliphatic poly (2 to 4)ol, and (II) a polyisocyanate compound (b) containing a diisocyanate compound.

Description

Urethane (meth)acrylate compound and resin composition containing same

technical field

The present invention relates to a urethane (meth)acrylate compound (A), a resin composition containing the compound, particularly a resin composition containing the urethane (meth)acrylate compound (A) and a photopolymerization initiator A resin composition, and a cured film of the resin composition, the urethane (meth)acrylate compound (A) is made of the following components as raw materials: containing dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra Dipentaerythritol poly( Meth)acrylate mixture (a). Moreover, the cured film of the resin composition of the present invention is excellent in hardness, adhesion to substrates, scratch resistance, etc., has little curl, and has little cracking, so it can be used as a plastic film or a small casing. hard coat.

In addition, since the cured film of the resin composition of the present invention has good adhesion to the substrate, has high hardness, and has moderate flexibility, the resin composition of the present invention can also be used for color filters ( For example, color filters used in color liquid crystal displays, color video cameras, color digital cameras, electronic paper, etc.), black matrix or spacers.

Background technique

Currently, lightweight and inexpensive plastics that are excellent in various properties such as processability, transparency, and optical properties are being effectively used in the industry. However, plastic has disadvantages such as being softer than glass, etc., and the surface is easily scratched, so a hard coating agent is usually applied to the surface of the plastic. As the hard coating agent, many thermosetting hard coating agents such as polysiloxane-based coatings, acrylic coatings, and melamine-based coatings are mainly known. Among them, polysiloxane-based hard coating agents have been mainly used so far because of their excellent performance and quality. However, this polysiloxane-based hard coat agent has disadvantages of long curing time and high cost.

Therefore, a photosensitive acrylic hard-coat agent has been developed and utilized as a hard-coat agent which makes up for the defect of a polysiloxane-type hard-coat agent (refer patent document 1). Since the acrylic hard coat agent is cured immediately when irradiated with radiation such as ultraviolet rays, the processing speed is fast, the hardness and scratch resistance are excellent, and it is inexpensive. Therefore, the acrylic hard coating agent has become the mainstream in the hard coating field at present. In particular, the acrylic hard coat agent is suitable for coating the surface of a base material such as polyester film during continuous processing.

Plastic substrate films include: polyester film, acrylic film, polycarbonate film, vinyl chloride film, triacetyl cellulose film, polyethersulfone film, etc. Among them, polyester films are most widely used from the viewpoint of various excellent properties. The polyester film can be used as an anti-scattering film for glass, a shading film for automobiles, a surface film for whiteboards, and an antifouling film for the overall kitchen surface. It can be used as a CRT flat-screen TV, touch panel, Functional thin film in liquid crystal display (LCD), plasma display (PDP), organic EL display, etc.

In addition to films, polyester resin moldings are widely used for the main body of home appliances, switches, mobile phones, personal computers, MP3 players and other electronic equipment casings. Any of them forms a hard coat layer so as not to scratch its surface. In addition, other than polyester, sheets or substrates such as hard-coated polycarbonate or acrylic are used for liquid crystal-related members in the periphery of optical disks or backlights.

In recent years, a thin film that imparts functions other than the so-called scratch resistance to the hard coat layer has also been developed. For example, in displays such as CRT, LCD, and PDP provided with a thin film, it is difficult to view the display screen due to reflection, and the eyes are prone to fatigue. Therefore, for example, in Patent Document 2, a hard coat layer with surface antireflection capability is also being developed.

In addition, on the other hand, researches on improving the hardness, which is the original purpose of the hard coat layer, are also being carried out. For example, in Patent Document 3, an increase in hardness is achieved by adding a polyfunctional urethane acrylate to a resin composition. However, there are problems in that the curing shrinkage of the polyfunctional urethane acrylate used is large, and the occurrence of cracks is observed.

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

prior art literature

Patent Document 1: Japanese Patent Application Laid-Open No. 9-48934

Patent Document 2: Japanese Patent Application Laid-Open No. 9-145903

Patent Document 3: Japanese Patent Laid-Open No. 2001-113648

Patent Document 4: Japanese Patent Laid-Open No. 2000-187102

Contents of the invention

The object of the present invention is to obtain a cured film, a urethane (meth)acrylate compound from which the cured film can be obtained, and a resin composition containing the compound. The hardness and scratch resistance of the cured film are It is excellent and less curling and cracking occur, which is better than the above-mentioned known cured film.

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, achieved the present invention.

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

(1) A urethane (meth)acrylate compound (A) obtained by making (I) any one of the following (i), (ii) or (iii) and (II) contain two The polyisocyanate compound (b) of the isocyanate compound is reacted to obtain:

(i) Contains a compound selected from the group consisting of dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate. Dipentaerythritol poly(meth)acrylate mixture (a) (hereinafter referred to as the mixture (a)) of at least two kinds of dipentaerythritol poly(meth)acrylates with a hydroxyl value of 80-120 mg KOH/g; or

(ii) both the mixture (a) and glycerin; or

(iii) All three of the mixture (a), glycerin, and (meth)acrylates of C2-C5 aliphatic polyhydric (2-4) alcohols.

(2) The urethane (meth)acrylate compound (A) as described in said (1) item whose (I) is (i) this mixture (a).

(3) The urethane (meth)acrylate compound (A) according to item (1) or (2) above, wherein (II) the polyisocyanate compound (b) is a diisocyanate compound alone or a diisocyanate compound For use in combination with a triisocyanate compound, the ratio of the diisocyanate compound to the triisocyanate compound is a ratio of 0 to 10 mol of the triisocyanate compound relative to 1 mol of the diisocyanate compound.

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

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

Y is an organic group represented by the following general formula (2), in which 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 above general formula (2), where 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 represented by the above general formula (2), where X in the formula is an isocyanate residue, c is 0, and a and b are the following (i) or (ii):

(i) When B exists at the end, a and b in the formula are integers of 1≤a≤5, 0≤b≤4, and a+b=5,

(ii) When B exists other than the terminal, a and b in the formula are integers of 1≤a≤4, 0≤b≤3, and a+b=4).

(5) The method for producing the urethane (meth)acrylate compound (A) according to any one of the above items (1) to (4), wherein the active hydrogen group in the mixture (a) is 1 Equivalent, the isocyanate group equivalent in the polyisocyanate compound (b) is the ratio of 0.1 to 50 equivalents, and (I) (i) this mixture (a) is made to react with (II) polyisocyanate compound (b).

(6) The urethane (meth)acrylate compound (A) according to item (1) or (3) above, wherein (I) is (ii) the mixture (a) and glycerin.

(7) The method for producing the urethane (meth)acrylate compound (A) of the above item (6), wherein the active hydrogen in glycerin is The group equivalent weight is 0.01～10 equivalents, the isocyanate group equivalent weight in (II) polyisocyanate compound (b) is the ratio of 0.1～50 equivalents, make this mixture (a) and glycerol in the above (1) item, and the above (1 ) in the (II) polyisocyanate compound (b) reaction.

(8) A resin composition comprising the urethane (meth)acrylate compound (A) and the (meth)acrylate (B) in any one of the above items (1) to (4) and (6). ) and photopolymerization initiator (C).

(9) The resin composition according to the above item (8), which is used for a hard coat layer.

(10) The urethane (meth)acrylate compound (A) according to item (1) or (3) above, wherein (I) is (iii) the mixture (a), glycerin, and C2-C5 fat Three types of (meth)acrylates of family poly(2-4) alcohols.

(11) The method for producing the urethane (meth)acrylate compound (A) according to the above item (1) or (10), wherein glycerol is The active hydrogen group equivalent of the active hydrogen group is 0.01 to 10 equivalents, the active hydrogen group equivalent of the (meth)acrylate of C2 to C5 aliphatic polyhydric (2 to 4) alcohol is 0.01 to 10 equivalents, the isocyanate group of the polyisocyanate compound (b) The equivalent is a ratio of 0.1 to 50 equivalents, so that (iii) the mixture (a), glycerol and (meth)acrylic acid ester of C2 to C5 aliphatic polyhydric (2 to 4) alcohols in (iii) of (I) of the above (1) item Three, react with (II) polyisocyanate compound (b) in item (1) above.

(12) The urethane (meth)acrylate compound (A) according to any one of the above items (1) to (4), (6) or (10), wherein the high performance liquid chromatography ( In terms of the area ratio (%) of HPLC), relative to the total amount of the mixture (a), the mixture (a) in (I) comprises 35 to 60% dipentaerythritol penta(meth)acrylate, in addition The total of the latter three of dipentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate is 90-100%, and the remaining 0-10% is more than dipentaerythritol tri(meth)acrylate and tripentaerythritol Polymer acrylate.

(13) The urethane (meth)acrylate compound (A) according to any one of the above items (1) to (4), (6), (10) or (12), wherein the polyisocyanate compound (b) is a diisocyanate compound alone.

(14) The urethane (meth)acrylate compound ( A) wherein the polyisocyanate compound (b) is used in combination of a diisocyanate compound and a triisocyanate compound.

(15) The urethane (meth)acrylate compound (A) according to the above item (13) or (14), wherein the diisocyanate compound is hexamethylene diisocyanate.

(16) The urethane (meth)acrylate compound (A) according to any one of the above items (1) to (4), (6), (10) and (12) to (14), wherein , the mixture (a) is a mixture of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, or dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and two The mixture of pentaerythritol hexaacrylate, the polyisocyanate compound (b) is hexamethylene diisocyanate alone, or both hexamethylene diisocyanate and hexamethylene diisocyanate trimer.

(17) A resin composition comprising the urethane (meth)acrylic acid according to any one of the above items (1) to (4), (6), (10) and (12) to (16) An ester compound (A) and a photopolymerization initiator (C).

(18) A cured film of a resin composition comprising any one of the above-mentioned (1) to (4), (6), (10) and (12) to (16) carbamate (methanol) base) acrylate compound (A) and photopolymerization initiator (C).

(19) The urethane (meth)acrylate compound (A) according to any one of the above items (1) to (4), (6), (10) and (12) to (16), wherein , The viscosity (60°C) is 5-40Pa·s.

Invention effect

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, which is less prone to curling and cracking, or to obtain a highly transparent A cured coating resin composition with moderate hardness, flexibility and toughness, a cured product of the resin composition, a hard coat agent containing the resin composition, and a hard coat layer using the hard coat agent.

Implementation

Hereinafter, the present invention will be described in detail.

In the present invention, as a raw material, a compound selected from the group consisting of dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate is used. dipentaerythritol poly(meth)acrylate mixture (a) {preferably comprising dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate The dipentaerythritol polyacrylate mixture (a')} of at least two of the group consisting of acrylates has a hydroxyl value in the range of 80 to 120 mg KOH/g. When the hydroxyl value is within this range, no gelation occurs during the urethanization reaction, and the target urethane (meth)acrylate compound (A) {preferably urethane acrylate Compound (A')}. Moreover, the hard-coat layer which has high hardness, excellent curl resistance, and high flexibility can be obtained from the resin composition containing the obtained urethane (meth)acrylate compound (A).

In addition, in this specification, when it is necessary to distinguish the above-mentioned urethane (meth)acrylate compound (A) by structure or composition, the compound that does not contain a skeleton derived from glycerin is referred to as urethane (meth)acrylate compound (A). base) acrylate compound (A1), a compound containing a glycerin-derived skeleton is called a urethane (meth)acrylate compound (A2), a glycerin-derived skeleton and a C2-C5 aliphatic The compound of the skeleton of the (meth)acrylate of polyhydric (2-4) alcohol is called a urethane (meth)acrylate compound (A3).

The above-mentioned dipentaerythritol poly(meth)acrylate mixture (a) (hereinafter also only referred to as poly(meth)acrylate mixture (a) or the mixture (a)) used as a raw material can be obtained by making dipentaerythritol and ( Meth)acrylic acid is obtained by carrying out a dehydration condensation reaction in the presence of a dehydration condensation catalyst, for example, an acid catalyst, and carrying out (meth)acrylic acid esterification of dipentaerythritol.

The mixture (a) preferably comprises dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate. At least three of the group, more preferably three comprising dipentaerythritol tetra, penta and hexa (meth)acrylates. Usually, the mixture (a) is a mixture containing four kinds of dipentaerythritol tri-, tetra-, penta-, and hexa(meth)acrylates, or a mixture containing three kinds of dipentaerythritol-tetra, penta, and hexa(meth)acrylates. This mixture (a) may further contain polymer acrylates of three or more pentaerythritols, such as tripentaerythritol, by-produced in the above-mentioned condensation reaction. In addition, among the above-mentioned (meth)acrylates of dipentaerythritol, acrylates (dipentaerythritol tri-, tetra-, penta-, and hexaacrylates) are more preferable than 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 (%) by high performance liquid chromatography (HPLC).

Dipentaerythritol penta(meth)acrylate (preferably dipentaerythritol pentaacrylate) is 30～70%, preferably 30～60%, more preferably 35～55%, more preferably 35～50%, in this dipentaerythritol penta(meth)acrylate base) acrylate (preferably dipentaerythritol pentaacrylate) plus dipentaerythritol tetra and hexa (meth) acrylate (preferably dipentaerythritol tetra and hexaacrylate) the total of the latter three is 85 to 100%, preferably 90% ~100%. In consideration of the by-products of the polymer produced during the dehydration condensation reaction, the total of the above three is 85 to 98%, preferably 90 to 97%. The rest comprises dipentaerythritol tri(meth)acrylate (preferably dipentaerythritol triacrylate) or/and acrylates of multipolymers of pentaerythritol terpolymer or higher. In addition, at this time, the respective contents of dipentaerythritol tetra and hexa(meth)acrylates are preferably about 1% to about 40% (preferably about 10% to about 30%), and about 15% to about 40% (preferably about 20% to about 40%), the content of dipentaerythritol tri(meth)acrylate is about 0% to about 10%, preferably 5% or less (including zero). In addition, acrylates of the above polymers may also be included.

The method for producing the above-mentioned mixture (a) will be described in detail below.

It is not limited thereto as long as the above-mentioned mixture (a) used as a raw material in the present invention can be obtained.

The acid catalysts used during the above-mentioned 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; Compounds and other Lewis acids; acid-type ion exchange resins, etc. These acid catalysts may be used alone or in combination of two or more. Among these, preferable catalysts include, for example, sulfuric acid.

The usage-amount of an acid catalyst is 0.01-50 mol% with respect to 1 mol of dipentaerythritol, Preferably it is 0.1-20 mol%.

In the dehydration condensation reaction of dipentaerythritol and (meth)acrylic acid, 0.1-20 mol of (meth)acrylic acid is used with respect to 1 mol of dipentaerythritol, Preferably it is 1-10 mol.

The reaction time in the dehydration condensation reaction can be in the range of 1 to 24 hours, and the reaction temperature can be in the range of 60 to 150°C. However, from the aspects of shortening the reaction time and preventing polymerization, it is preferably carried out at 75 to 120°C, more preferably Carry out at 100-120°C.

The reaction solvent in the dehydration condensation reaction is preferably an azeotropic solvent from which water generated during the reaction can be distilled off. The azeotropic solvent mentioned here preferably has a boiling point of 60 to 130°C, can azeotrope with water and can be easily separated from water.

Specifically, it is desirable to use one or a mixture of two or more non-reactive organic solvents such as benzene, toluene, n-hexane, n-heptane, and cyclohexane. Toluene is generally more preferred. The amount used is arbitrary, but is preferably 10 to 70% by mass based on the reaction mixture.

Commercially available (meth)acrylic acid used as a raw material usually has a polymerization inhibitor such as 4-methoxyphenol added, but the polymerization inhibitor may be newly added during the reaction. Examples of such polymerization inhibitors include, for example, hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5 -Dihydroxy-p-benzoquinone, phenothiazine, etc. In addition, chlorinated ketones can also be used. The usage-amount is 0.01-1 mass % with respect to a reaction mixture.

The urethane (meth)acrylate compound (A) of the present invention can be obtained by making (I) the following (i), (ii) or (iii),

(i) Contains a compound selected from the group consisting of dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate. Dipentaerythritol poly(meth)acrylate mixture (a) (hereinafter referred to as the mixture (a)) of at least two kinds of dipentaerythritol poly(meth)acrylates with a hydroxyl value of 80-120 mg KOH/g; or

(ii) both the mixture (a) and glycerol; or

(iii) The mixture (a), glycerin and (meth)acrylates of C2-C5 aliphatic polyhydric (2-4) alcohols

Any one of (hereinafter also referred to as (I) component), and

(II) It is obtained by reacting the polyisocyanate compound (b) containing a diisocyanate compound.

The polyisocyanate compound (b) used in the manufacture of the urethane (meth)acrylate compound (A) of the present invention can be used as long as it contains two or more isocyanate groups in one molecule, but It is necessary to contain a diisocyanate compound in the present invention. The polyisocyanate compound (b) is preferably a diisocyanate compound alone or a combination of a diisocyanate compound and another polyisocyanate. When using this combination, the combined use of a diisocyanate compound and a triisocyanate compound is especially preferable.

The polyisocyanate compound (b) that can be used in the present invention includes, for example, aliphatic polyisocyanate compounds, aromatic polyisocyanate compounds, alicyclic polyisocyanates, trimer or polymer compounds thereof, dimer Urea-type polyisocyanate, allophanate-type polyisocyanate, etc. A trimer or polymer compound refers to a compound in which three isocyanate groups form one or two 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 used in combination with a diisocyanate compound and other polyisocyanate compounds. In addition, the combined use of a diisocyanate compound and another polyisocyanate compound is preferably a combined use of a diisocyanate compound and a triisocyanate compound, and in this case, any of them may be one or more of each. Usually, one of each is preferred.

Aliphatic polyisocyanate compounds include, for example, hexamethylene diisocyanate (1,6-hexamethylene diisocyanate), isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, Hydrogenated diphenylmethane diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanato, 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-methylene bis(cyclo C4-C12 aliphatic di- or triisocyanate compounds such as hexyl isocyanate), lysine diisocyanate, norbornane diisocyanate, dicycloheptane triisocyanate, trimer of hexamethylene diisocyanate, etc.

Aromatic polyisocyanate compounds include, for example, toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, benzylidine diisocyanate, 1,4-phenylene diisocyanate, Diisocyanate, 1,6-phenylene diisocyanate, 3-tetramethylxylene diisocyanate, 4-tetramethylxylene diisocyanate, etc. C6 having 1 to 2 phenylene rings or 1 naphthalene ring ~C13 aromatic diisocyanate.

Among the above-mentioned polyisocyanates (b), in the present invention, it is preferable to use a diisocyanate compound alone or a combination of a diisocyanate compound and a triisocyanate compound.

The ratio of diisocyanate compound and other polyisocyanate compound, preferably triisocyanate compound is relative to 1 mole of diisocyanate compound, other polyisocyanate compound (preferably triisocyanate compound) is about 0 mol～about 10 mol, preferably about 0 mol～about 7 mol. mol, more preferably about 0 mol to about 5 mol, even more preferably about 0 mol to about 3 mol.

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

The ratio of the polyisocyanate compound (b) to the mixture (a) is 1 equivalent of active hydrogen groups in the mixture (a) (the dipentaerythritol poly(meth)acrylate mixture (a)), The isocyanate group equivalent is usually in the range of 0.1 to 50 equivalents, preferably in the range of 0.1 to 10 equivalents. When reacting glycerin, the active hydrogen group equivalent of glycerol is usually in the range of 0.01 to 10 equivalents, preferably in the range of 0.1 to 1 equivalent, relative to 1 equivalent of active hydrogen groups in the poly(meth)acrylate mixture (a). .

In addition, the active hydrogen group in the mixture (a) refers to the hydrogen atom in the hydroxyl group, and the active hydrogen group in the (meth)acrylate of glycerin and C2～C5 aliphatic polyhydric (2～4) alcohol also refers to the hydrogen atom in the hydroxyl group. Hydrogen atoms in the hydroxyl groups in the respective compounds. In addition, in this invention, the term so-called hydroxyl group equivalent is also used, and it is used for the same meaning as active hydrogen group equivalent.

In addition, the usage ratio of the polyisocyanate compound (b) to 1 mole of the mixture (a) is based on the hydroxyl equivalent weight of the mixture (a), the isocyanate group equivalent weight in the polyisocyanate compound (b), and glycerol and C2-C5 fatty acids. (Meth)acrylic acid esters of group poly(2-4) alcohols vary depending on whether they are used in combination or not, so it cannot be generalized, but it is preferably in the range of about 0.3 mol to about 1 mol with respect to 1 mol of the mixture (a), The polyisocyanate compound (b) is preferably used in the range of about 0.3 mol to about 0.9 mol, more preferably in the range of 0.33 to 0.8 mol.

For example, when the above-mentioned (I) component is (i) when the mixture (a) is alone, about 0.3 mol to about 0.7 mol of the polyisocyanate compound (b) is used, preferably about 0.33 mol to 1 mol of the mixture (a). About 0.6 moles.

In addition, when the above-mentioned component (I) is (ii) or (iii) (when the mixture (a) is used in combination with glycerin), it is more preferable to increase the polyisocyanate compound (b) depending on the number of moles of glycerin used in combination. ) usage. The amount of the polyisocyanate compound (b) to be increased is preferably in the range of about half to about one time the number of moles of glycerin used. For example, when glycerol is used in combination in a ratio of about 0 mol to about 0.3 mol, preferably about 0 mol to about 0.2 mol, relative to 1 mol of the mixture (a), the increase in polyisocyanate compound (b) (preferably diisocyanate compound The amount of alone or in combination of a diisocyanate compound and a triisocyanate compound) is about 0 mol to 0.3 mol, more preferably about 0 mol to 0.2 mol, based on 1 mol of the mixture (a). Moreover, when the (meth)acrylate of C2-C5 aliphatic polyhydric (2-4) alcohol has a hydroxyl group, it is preferable to increase polyisocyanate compound (b) so that NCO equivalent number may correspond to the hydroxyl group equivalent number. Usually, it is preferable that the total equivalents of the active hydrogen groups of the components in the mixture (a) be the same as the equivalents of NCO of the reacted polyisocyanate compound (b), or that the equivalents of NCO be within 0.1%. amount to react.

In addition, 1 mole of the mixture (a) in this specification means the content ratio (mole number) multiplied by the respective molecular weights and defined as the molecular weight of the mixture (a).

In addition, (meth)acrylic acid esters of C2-C5 aliphatic polyhydric (2-4) alcohols used in (iii) of (I) include, for example, C2-C5 aliphatic polyhydric (2-4) alcohols such as ethylene glycol, propylene glycol, and pentaerythritol. (2-4) The (meth)acrylate obtained by reaction of alcohol and (meth)acrylic acid. The (meth)acrylate preferably contains 30 to 100% by mass, preferably 50 to 100% by mass, of the (meth)acrylate having a hydroxyl group relative to the total amount of the (meth)acrylate (the rest are those that do not have a hydroxyl group Acrylates of C2-C5 aliphatic polyhydric (2-4) alcohols). Preferred (meth)acrylates include, for example, hydroxyethyl (meth)acrylate, poly(2-4) (meth)acrylates of pentaerythritol (preferably pentaerythritol di- or tri-(meth)acrylate and pentaerythritol tetra (Meth) acrylate mixture), more preferably hydroxyethyl acrylate, or pentaerythritol tri- and tetra-acrylate mixture (for example, mixing ratio (mass) three: four = 1: 0.01 ~ 1, preferably 1: 0.1 ~ 0.6) .

The reaction of (I) component and (II) polyisocyanate (b) containing this mixture (a) can be performed similarly to normal urethanization reaction. This reaction can also be performed in the presence of an inert organic solvent, such as a ketone solvent such as methyl ethyl ketone, and a catalyst as needed.

The reaction temperature is usually in the range of 30 to 150°C, preferably in the range of 50 to 100°C. Regarding the end point of the reaction, the remaining isocyanate group (NCO) was reacted with excess n-butylamine and back-titrated with 1N hydrochloric acid to calculate the residual isocyanate group (NCO) content, and the polyisocyanate ( In b) the isocyanate group (NCO) content, the time when the residual isocyanate group (NCO) content becomes 0.5% or less, preferably 0.1% or less is defined as an end point.

In order to shorten their reaction time, catalysts can be added. As this catalyst, any one of a basic catalyst and an acidic catalyst can be used.

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

In addition, acidic catalysts, such as metal alkoxides such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, tetrabutoxytitanium, and tetrabutoxyzirconium, Lewis catalysts such as aluminum chloride, etc. Acids, tin 2-ethylhexanoate, octyltin trilaurate, dibutyltin dilaurate, octyltin diacetate and other tin compounds. Acidic catalysts of tin compounds are preferred, more preferably dibutyltin dilaurate.

The addition amount of these catalysts is 0.1 mass part or more and 1 mass part or less normally with respect to 100 mass parts of polyisocyanate compounds (b).

In addition, during the reaction, in order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (such as 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 3-hydroxythiophenol, p- Benzoquinone, 2,5-dihydroxy-p-benzoquinone, phenothiazine, etc.), the amount of the polymerization inhibitor used is 0.01 mass % or more and 1 mass % or less, preferably 0.05 mass % or more and 0.5% by mass or less.

The urethane (meth)acrylate compound (A) obtained by the method described above is not a single urethane compound, but a urethane having different degrees of polymerization, etc. obtained as a mixture of compounds. In particular, in the presence of glycerin or, and (meth)acrylic esters of C2-C5 aliphatic polyhydric (2-4) alcohols, the poly(meth)acrylate mixture (a) is mixed with the polyisocyanate compound ( b) The product during the reaction becomes a complex polycondensate mixture (urethane (meth)acrylate compound).

The viscosity (60° C.) of the obtained urethane (meth)acrylate compound (A) is about 5 Pa·s to about 40 Pa·s, preferably about 10 Pa·s to about 38 Pa·s, more preferably about 12 Pa·s s to about 38 Pa·s, most preferably about 14 Pa·s to about 35 Pa·s. In addition, among the most preferable viscosities, the curling property is less when the viscosity is 15 Pa·s or more, the curling property is even less when the viscosity is 17 Pa·s or more, and the curling property is the least when the viscosity is 18 Pa·s or more.

In addition, 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 with less curl, the weight average molecular weight is about 7,000 to about 50,000, preferably about 7,000 to about 35,000.

In addition, the number average molecular weight is about 1400 to 2500, preferably about 1500 to 2300, more preferably about 1600 to 2300, further preferably about 1700 to 2300, and most preferably about 1700 to 2100.

One of the more preferable aspects of the urethane (meth)acrylate compound (A) is that the weight average molecular weight is about 4,500 to about 35,000, the number average molecular weight is about 1,500 to about 2,300, and the viscosity (60° C.) is about 5 Pa ·s～approximately 40Pa·s. In addition, one of the more preferable aspects is that the weight average molecular weight is about 7000 to about 35000, the number average molecular weight is about 1700 to about 2300, and the viscosity (60° C.) is about 12 Pa·s to about 35 Pa·s.

In addition, the urethane (meth)acrylate compound of the present invention generally contains about 60% to about 90%, preferably About 60% to about 85% urethanized (meth)acrylate (urethane (meth)acrylate), the remaining about 10% to about 40%, preferably about 15% to about 40% Contains non-urethanized (meth)acrylates (unreacted dipentaerythritol hexa(meth)acrylate derived from raw materials and non-urethanized pentaerythritol polymers (polymers of three or more things, etc.).

Glycerin and (meth)acrylic esters of C2-C5 aliphatic polyhydric (2-4) alcohols are not allowed to coexist, and the multi-(meth)acrylate mixture (a) and the difunctional polyisocyanate compound (b) ( When a diisocyanate compound) reacts, it will become the urethane (meth)acrylate compound (A1) represented by 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) When Y represents an organic group represented by general formula (2), X is an isocyanate residue, a, b and c are positive integers, a+b+c=4, 1≤a≤4, 0≤b ≤3 and 0≤c≤3, Y is a divalent group,

(2) When A represents an organic group represented by general formula (2), or when B is present at the terminal, c is 0, X is an isocyanate residue, a and b are 1≤a≤5, 0≤b≤4 Integer of , and a+b=5,

(3) When B exists 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. However, when B is present at other than the terminal, theoretically, B independently represents the same group as Y, but it is represented as above for the sake of simplicity in the specification of the present application.

Therefore, when Y represents an organic group represented by general formula (2) and when B exists other than the terminal, it is a divalent group independently represented by general formula (2), and A represents a group represented by general formula (2). When the organic group is present and when B is present at the terminal, they are each independently, and the general formula (2) is a monovalent group.

In the case of (2) above (when A represents an organic group represented by general formula (2), or when B is present at the terminal), formula (2) can be represented by the following formula (2a).

In the formula, a' and b' are positive integers, 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 may also appropriately contain (meth)acrylate (B), curing accelerator (D), diluent (E), and other ingredients.

Examples of other components include leveling agents, defoamers, ultraviolet absorbers, photostabilizers, antioxidants, polymerization inhibitors, and crosslinking agents.

The resin composition of the present invention is a photosensitive resin composition that can be cured by irradiating energy rays such as ultraviolet rays.

In addition, the resin composition of the present invention preferably contains an organic solvent as a diluent (E) in order to easily form a film such as a hard coat layer.

In the resin composition of the present invention, the content of the urethane (meth)acrylate compound (A) of the present invention is, when the solid content of the resin composition of the present invention is 100% by mass, usually 5 to 97% by mass, preferably 20 to 80% by mass, and depending on circumstances, preferably about 40% by mass to about 95% by mass, more preferably about 50% by mass to about 95% by mass, most preferably about 70% by mass to about 95% by mass .

In addition, the content of the urethane (meth)acrylate compound (A) relative to the total amount of the resin composition of the present invention is usually 5 to 97% by mass, preferably about 20% by mass to 95% by mass, and more preferably Preferably it is about 40 mass % - about 95 mass %, More preferably, it is about 45 mass % - about 95 mass %.

The (meth)acrylate (B) which can be used in this invention includes (meth)acrylate compounds other than the said urethane (meth)acrylate compound (A), for example. For example, mono(meth)acrylate (acrylic ester with 1 acryloyl group) or polyacrylate (difunctional (meth)acrylate or trifunctional (meth)acrylate: having 2 or more Acryloyl acrylate), etc. Polyester (meth)acrylate and urethane (meth)acrylate oligomers are also included in the polyacrylate (except for the urethane (meth)acrylate compound (A)) , polyester (meth)acrylate oligomer or epoxy (meth)acrylate oligomer, etc. These can be used individually or in mixture of 2 or more types.

In this invention, the poly(meth)acrylate compound which has 2-6 (meth)acryloyl groups is preferable. Preferred multi-(meth)acrylate compounds include, for example, C1-C12 aliphatic diol di(meth)acrylates or dipentaerythritol poly(3-6) (meth)acrylates, more preferably, for example, C1-C12 aliphatic diol diacrylate or dipentaerythritol poly(3-6) acrylate.

C1-C12 aliphatic diol diacrylate is preferably C1-C6 aliphatic diol diacrylate.

When it is desired to obtain a flexible film, C1-C12 aliphatic diol diacrylate is preferred, and when it is desired to obtain a cured product with high hardness, dipentaerythritol poly(3-6) acrylate is preferred.

In addition, in the present invention, expressions such as "(meth)acrylate" may have a methyl group. For example, "(meth)acrylate" may be used to indicate acrylate or methacrylate. In addition, expressions such as "many (3-6)" or "many (2-4)" mean that "many" is "3-6" or "2-4".

Mono(meth)acrylates include, for example, acryloyl morpholine; hydroxyl-containing (meth)acrylates such as 2-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; cyclohexyl Alkane-1,4-dimethanol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate , dicyclopentadienyl (meth)acrylate, dipolycyclopentadienyloxyethyl (meth)acrylate and other aliphatic (meth)acrylates; phenoxyethyl (meth)acrylate , phenyl (poly)ethoxy (meth)acrylate, 4-cumylphenoxyethyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, benzene (meth)acrylate Thioethyl ester, 2-Hydroxy-3-phenoxypropyl (meth)acrylate, Phenylphenol (poly)ethoxy (meth)acrylate, Phenylphenol epoxy (meth)acrylate and other aromatic (meth)acrylates.

Difunctional (meth)acrylates, can enumerate 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 Acrylates, bisphenol F (poly)ethoxy di(meth)acrylate, ethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate hydroxytrimethylacetate Di(meth)acrylates of ε-caprolactone adducts of pentanediol esters (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-620, etc.), bisphenol A diepoxy acrylic acid Epoxy acrylate, etc.

Trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, trimethyloloctane Tri(meth)acrylate, Trimethylolpropane(poly)ethoxytri(meth)acrylate, Trimethylolpropane(poly)propoxytri(meth)acrylate, Trimethylolpropane(poly)propoxytri(meth)acrylate, Trimethylolpropane(poly)ethoxytri(meth)acrylate Propane(poly)ethoxy(poly)propoxy tri(meth)acrylate and other methylol-based poly(meth)acrylates; pentaerythritol tri(meth)acrylate, pentaerythritol(poly)ethoxylate Tetra(meth)acrylate, Pentaerythritol (poly)propoxy tetra(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Dipentaerythritol tetra(meth)acrylate, Dipentaerythritol penta(meth)acrylate Erythritol poly(meth)acrylates such as dipentaerythritol hexa(meth)acrylate; Tris[(meth)acryloyloxyethyl]isocyanurate, caprolactone modified (Multi)(meth)acrylate isocyanurates such as tris[(meth)acryloyloxyethyl]isocyanurate.

As (poly)ester (meth)acrylate, the di(meth)acrylate of (poly)ester diol etc. are mentioned, for example.

(Poly)ester diol can be obtained by reaction of a diol compound and a dibasic acid or its anhydride.

Above-mentioned glycol compound can enumerate glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, (poly) ethylene glycol, (poly) propylene glycol; , 4-butanediol, 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 and other linear or branched alkyl glycols; Alicyclic alkyl glycols such as cyclohexane-1,4-dimethanol; bisphenol A (poly)ethoxylated diol, bisphenol A (poly)propoxylated diol, and the like.

Examples of the dibasic acid or its anhydride include succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, and anhydrides thereof.

The above-mentioned urethane (meth)acrylate oligomer can be exemplified by adding a hydroxyl group-containing (meth)acrylate to a reaction product of a diol compound (including the above-mentioned polyester diol) and an organic polyisocyanate. Obtained urethane (meth)acrylate oligomer etc. (However, the said urethane (meth)acrylate (A) is excluded).

The diol compound can be, for example, (poly)ethylene glycol (such as ethylene glycol, diethylene glycol, triethylene glycol, or polyethylene glycol with a higher degree of polymerization), (poly)propylene glycol (such as propylene glycol, diethylene glycol, Propylene glycol, tripropylene glycol, or propylene glycol with 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-dimethanol and other C1-C12 aliphatic diols or poly(C2-C4 alkylene) glycols; bisphenol A (poly)ethoxy Bisphenol A (poly) C2-C3 alkoxy diols such as diol or bisphenol A (poly) propoxy diol; or polyester diols as reactants of these diol compounds with dibasic acids or their anhydrides Alcohol etc. In addition, examples of the dibasic acid or its anhydride include succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, or their anhydrides.

Examples of organic polyisocyanates used in the synthesis of the aforementioned urethane (meth)acrylate oligomers include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and other chain saturated hydrocarbon isocyanates; isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, Cyclic saturated hydrocarbon isocyanates such as methyl bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate; 2,4-toluene diisocyanate, 1,3-benzenediisocyanate Methylene diisocyanate, 4-phenylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenylene diisocyanate, 1 , Aromatic polyisocyanates such as 5-naphthalene diisocyanate, etc.

The above-mentioned (poly)ester (meth)acrylate oligomers include, for example, (poly)ester (meth)acrylate oligomers obtained by reacting the above-mentioned polyester diol with (meth)acrylates, etc. .

In addition, examples of the epoxy (meth)acrylate oligomer include epoxy (meth)acrylate oligomers obtained by reacting an epoxy resin and (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 above-mentioned (meth)acrylate (B) is such that when the solid content of the resin composition of the present invention is 100% by mass, the ratio thereto is usually 0% by mass or more. And 94% by mass or less, preferably 0 to 60% by mass, in use as long as it is greater than zero, preferably 5 to 60% by mass, more preferably 10 to 60% by mass. Moreover, 20-80 mass % is also preferable as the case may be.

Moreover, content of (meth)acrylate (B) with respect to the resin composition whole quantity of this invention is about 0 mass % - about 50 mass % normally, Preferably it is about 0 mass % - about 40 mass %, More preferably, it is about 0 mass %. Mass% to about 30 mass%, as long as it is greater than zero when used, preferably 3 to 50 mass%, more preferably 5 to 40 mass%, even more preferably 5 to 30 mass%.

The photopolymerization initiator (C) used in the resin composition of the present invention includes, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin iso Benzoins such as butyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methylphenyl Propan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -Acetophenones such as ketones; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone and other anthraquinones; 2,4-diethylthioxanthone , 2-isopropylthioxanthone, 2-chlorothioxanthone and other thioxanthones; acetophenone dimethyl ketal, biphenyl dimethyl ketal and other ketals; benzophenone, 4 - Benzoyl-4'-methyl diphenyl sulfide, 4,4'-bis(methylamino)benzophenone and other benzophenones; 2,4,6-trimethylbenzoyl diphenyl Phosphine oxides such as phenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and the like. In addition, specifically, Irgacure ^RTM 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 907 (2-methyl-1-(4-(methyl (thio)phenyl)-2-morpholinopropan-1-one), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) manufactured by BASF Corporation, and the like. In addition, these can be used individually or in mixture of 2 or more types. Among them, photopolymerization initiators belonging to acetophenones are preferred, and 1-hydroxycyclohexyl phenyl ketone (Irgacure ^RTM ) is more preferred.

In the resin composition of the present invention, the content of the photopolymerization initiator (C) is 0.1% by mass to 10% by mass, preferably 1% by mass, when the solid content of the resin composition of the present invention is 100% by mass. Mass % or more and 7 mass % or less.

Moreover, content of this photoinitiator (C) can be about 0.2 mass % - about 12 mass % with respect to 100 mass % of solid content of the resin composition of this invention. In this case, it is preferably about 0.5% by mass to about 10% by mass, more preferably about 1% by mass to about 10% by mass, further preferably about 2% by mass to about 8% by mass.

Moreover, the said photoinitiator (C) can also be used together with a hardening accelerator (D). The curing accelerator (D) that can be used in combination includes, for example, triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethyl benzoate, dimethylaminoacetophenone, and 4-dimethylaminobenzoic acid Amines such as isoamyl ester and EPA, and hydrogen donors such as 2-mercaptobenzothiazole. The usage-amount of these hardening accelerators is 0 mass % or more and 5 mass % or less when the solid content of the resin composition of this invention is 100 mass %. These can be used individually or in mixture of 2 or more types.

The diluent (E) can be used for the resin composition of this invention as needed. As the diluent (E), a solvent that is liquid at normal temperature (20° C.), usually an organic solvent, is used. For example, lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-enantholactone, α-acetyl-γ-butyrolactone, and ε-caprolactone can be listed; Alkanes, 1,2-Dimethoxymethane, Diethylene Glycol Dimethyl Ether, Diethylene Glycol Diethyl Ether, 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 and other ethers; ethylene carbonate, propylene carbonate, etc. Carbonates; ketones such as methyl ethyl ketone (2-butanone), methyl isobutyl ketone, cyclohexanone, and acetophenone; phenols such as phenol, cresol, and xylenol; ethyl acetate, butyl acetate, Ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate and other esters; toluene, Hydrocarbons such as xylene, diethylbenzene, and cyclohexane; halogenated hydrocarbons such as trichloroethane, tetrachloroethane, and monochlorobenzene; petroleum solvents such as petroleum ether and naphtha; 2H, 3H-tetrafluoropropane Fluorine-containing alcohols such as alcohol; hydrofluoroethers such as perfluorobutyl methyl ether and perfluorobutyl ethyl ether; alcohols such as methanol, ethanol, isopropanol, and n-propanol; both ketone and alcohol properties diacetone alcohol etc. These can be used individually or in mixture of 2 or more types.

Among them, ester solvents such as ethyl acetate (preferably acetates of C2-C3 alcohols) 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 above-mentioned diluent (E) is in the range of about 0 mass % to about 90 mass %, preferably about 0 mass % to about 80 mass %, relative to the total amount of the resin composition of the present invention %, more preferably about 0% by mass to 60% by mass.

In addition, 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% by mass to 300% by mass, preferably about 0% by mass to 200% by mass, more preferably About 0% by mass to about 150% by mass.

In this specification, the content expressed by including 0, such as "0 to 90% by mass" as described above in terms of the content of the components of the composition, means that the component is not included, or the content is greater than 0 and 90% by mass or less. range contains.

In addition, the resin composition of the present invention may contain a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, and the like as other additives other than the above, as required. By including them, target functionality can be imparted, respectively.

Leveling agents can include, for example, fluorine-containing compounds, polysiloxane compounds, acrylic compounds, etc., UV absorbers can include, for example, benzotriazole compounds, benzophenone compounds, triazine compounds, etc. Agents can include, for example, steric compounds, benzoate compounds, etc. Antioxidants can include, for example, phenolic compounds, etc., polymerization inhibitors can include, for example, methoquinone, methyl hydroquinone, hydroquinone, etc., and crosslinking agents can include, for example, The polyisocyanates, melamine compounds, etc.

One of the preferred resin compositions of the present invention contains the urethane (meth)acrylate compound (A) of the present invention and a photopolymerization initiator (C), and further contains (meth)acrylate (B) or a resin composition of at least any one of diluents (E).

More specifically, preferable resin compositions of the present invention are listed below. The composition ratio is a ratio relative to the solid content of the resin composition being 100% by mass.

(i) a resin composition comprising:

5-97% by mass of urethane (meth)acrylate compound (A),

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

0 to 50% by mass of (meth)acrylate (B), and

0-300 mass % diluent (E), and this diluent (E) is an organic solvent.

(ii) The resin composition as described in said (i) which contains 40-95 mass % of urethane (meth)acrylate compounds (A).

(iii) The resin composition according to (i) or (ii) above, which contains 5 to 40% by mass of (meth)acrylate (B), or 50 to 150% by mass of organic diluent (E) at least any one of the solvents.

(iv) The resin composition according to any one of (i) to (iii) above, wherein the urethane (meth)acrylate compound (A) is the above (1) to (4), ( 5), the urethane (meth)acrylate compound (A) described in any one of (10), (12) to (16) and (19), or the above (5), (7) Or the urethane (meth)acrylate compound (A) manufactured by the manufacturing method as described in any one of (11).

(v) The resin composition as described in any one of said (i)-(iv) whose photoinitiator (C) is a photoinitiator belonging to acetophenones.

(vi) The resin composition described in any one of (i) to (v) above, wherein the (meth)acrylate (B) is C1 to C12 aliphatic diol di(meth)acrylate or Dipentaerythritol poly(3-6) (meth)acrylate.

(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 for a hard coat layer (hard coat agent), and can also be used as a molding material for components for electrical products and electronic components described later.

The resin composition of this invention can be obtained by mixing the said (A) component and (C) component, and as needed (B) component, (D) component, (E) component, and other components in arbitrary order.

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

More specifically, it can be applied by using a bar coater or the like so that the film thickness after drying may be 0.1 μm to 300 μm, usually 0.1 μm to 50 μm, more preferably 1 μm to 20 μm The above-mentioned resin composition is obtained by drying and then irradiating with ultraviolet rays to form a cured film if necessary.

The film thickness after curing varies depending on the application, and the film thickness after curing is about 0.1 μm to about 300 μm, preferably about 1 μm to about 250 μm. When forming a coating film on a base film, the film thickness after curing is generally 0.1 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 10 μm, and even more preferably 7 μm or less.

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

The above-mentioned coating method of the resin composition includes, for example, bar coater coating, wire bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, micro reverse gravure coating Box coating, die slot coater coating, dip coating, spin coating, spray coating, etc.

For curing, ultraviolet rays may be irradiated, electron beams or the like may be used. When curing by ultraviolet rays, the light source can use ultraviolet irradiation devices such as xenon lamps, high-pressure mercury lamps, and metal halide lamps, and the amount of light and the arrangement of the light source can be adjusted as needed. When using a high-pressure mercury lamp, it is preferable to perform curing at a transport speed of 5 to 60 m/min per one lamp having an energy of 80 to 120 W/cm ² . Moreover, when hardening by an electron beam, it is preferable to use the electron beam accelerator which has energy of 100-500 eV, In this case, you may not use a photoinitiator (C).

The cured film of the resin composition of the present invention can be suitably used also as a material for a display device because it has adhesion to a substrate, hardness, and moderate flexibility. For example, materials for color filters used in LCD, EL, rear projection display, electronic paper, etc., separator materials for dividing fine display elements used in PDP, electronic paper, etc., used in LCD, FED (SED), etc. A spacer (functioning as a pillar for maintaining a distance), or a solid-state imaging element such as a digital camera, etc. The cured product of the photosensitive resin composition of the present invention is particularly suitable as a resin for color filters such as liquid crystal display devices or solid-state imaging devices such as digital cameras, and among them, it is particularly suitable as a color filter. This color filter has patterned multi-color colored pixels, black matrix, and spacers made of the cured product of the photosensitive resin composition of the present invention produced by the method described above.

In the present invention, the display device is an example of a liquid crystal display device, such as 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 polarizing film, etc. The structure obtained by stacking in the above-mentioned order was fabricated. In addition, taking a solid-state imaging device as an example, a color filter layer using the photosensitive resin composition of the present invention is provided on a silicon wafer provided with a transfer electrode and a photodiode, and then a microlens is laminated.

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

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. In addition, unless otherwise stated in an Example, a part means a mass part. In addition, in the Examples, the abbreviations used are as follows.

DPETtriA: dipentaerythritol triacrylate

DPETtetraA: dipentaerythritol tetraacrylate

DPETpentaA: dipentaerythritol pentaacrylate

DPEThexaA: dipentaerythritol hexaacrylate

TPETA: Polymer acrylate of tripentaerythritol or higher

HPLC: High Performance Liquid Chromatography

GPC: Gel Permeation Chromatography

In addition, HPLC and GPC measurement conditions are as follows.

HPLC determination conditions

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

Detector: UV 254nm

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

Column temperature: 40°C

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

Flow rate: 0.6ml/min

Injection volume: 2μl

Sample concentration: 1% by weight

GPC measurement conditions

Device: TOSOH HLC-8220GPC

Detector: RI

Column: TOSOH TSK-GEL SUPER HZM-N

Column temperature: 40°C

Eluent: THF

Flow: 0.35ml/min

Injection volume: 5μl

Sample concentration: 1% by weight

Raw material synthesis example 1

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature regulator, and a water separator, add 254.3 g (1.0 mol) of dipentaerythritol, 449.7 g (6.2 mol) of acrylic acid, 9.81 g of sulfuric acid, and 1.03 g of chlorinated ketones , 424.7 g of toluene, heated the reactor, and reacted for 12 hours while the generated water and the solvent were removed by azeotropic distillation. After the reaction, 849.4 g of toluene was added for dilution, and after neutralizing with 25% NaOH aqueous solution, it washed 3 times with 600 g of 15 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 terms of area ratio (%) by high performance liquid chromatography (HPLC) was 10:43:37:10. In addition, the viscosity of this mixture was 6300 mPa·s (25 degreeC).

Raw material synthesis example 2

In the reactor equipped with reflux condenser, stirrer, thermometer, temperature regulator, and water separator, add dipentaerythritol 254.3g (1.0mol), acrylic acid 432.4g (6.0mol), sulfuric acid 9.81g, chlorinated ketone 0.99g , 424.7 g of toluene, heated the reactor, and reacted for 12 hours while the generated water and the solvent were removed by azeotropic distillation. After the reaction, 849.4 g of toluene was added and diluted, and after neutralizing with 25% NaOH aqueous solution, it washed 3 times with 600 g of 15 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 terms of the area ratio (%) of HPLC was 12:45:36:7. In addition, the viscosity of this mixture was 6300 mPa·s (25 degreeC).

Raw material synthesis example 3

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature regulator, and a water separator, add 254.3 g (1.0 mol) of dipentaerythritol, 402.1 g (5.6 mol) of acrylic acid, 9.81 g of sulfuric acid, and 0.92 g of chlorinated ketones , 424.7 g of toluene, heated the reactor, and reacted for 12 hours while the generated water and the solvent were removed by azeotropic distillation. After the reaction, 849.4 g of toluene was added and diluted, and after neutralizing with 25% NaOH aqueous solution, it washed 3 times with 600 g of 15 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 mg KOH/g, hydroxyl equivalent: 467.6 g/Eq).

The ratio of each component of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA in terms of the area ratio (%) of HPLC was 3:26:41:24:6. In addition, the viscosity of the mixture was 6000 mPa·s (25° C.).

Comparative raw material synthesis example 1

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature regulator, and a water separator, add 254.3 g (1.0 mol) of dipentaerythritol, 497.2 g (6.9 mol) of acrylic acid, 9.81 g of sulfuric acid, and 1.41 g of chlorinated ketones , 424.7 g of toluene, heated the reactor, and reacted for 12 hours while the generated water and the solvent were removed by azeotropic distillation. After the reaction, 849.4 g of toluene was added and diluted, and after neutralizing with 25% NaOH aqueous solution, it washed 3 times with 600 g of 15 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 terms of the area ratio (%) of HPLC was 2:30:56:12. In addition, the viscosity of this mixture was 6500 mPa·s (25 degreeC).

Comparative raw material synthesis example 2

In the reactor equipped with reflux condenser, stirrer, thermometer, temperature regulator, and water separator, add dipentaerythritol 254.3g (1.0mol), acrylic acid 380.5g (5.3mol), sulfuric acid 9.81g, chlorinated ketone 0.88g , 424.7 g of toluene, heated the reactor, and reacted for 12 hours while the generated water and the solvent were removed by azeotropic distillation. After the reaction, 849.4 g of toluene was added and diluted, and after neutralizing with 25% NaOH aqueous solution, it washed 3 times with 600 g of 15 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 mg KOH/g, hydroxyl equivalent: 400.8 g/Eq).

The ratio of each component of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA and TPETA in terms of the area ratio (%) of HPLC was 4:30:42:19:5. In addition, the viscosity of this mixture was 5800 mPa·s (25 degreeC).

Embodiment A (synthesis example 1)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 1 (hydroxyl value: 80mg KOH/g, hydroxyl equivalent: 701.4g/ Eq) 446.47g (0.64mol), 0.25g of 4-methoxyphenol as a polymerization inhibitor, 0.25g of dibutyltin dilaurate as a urethane reaction catalyst and stir until uniform, so that the internal temperature is 50°C . Next, 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, it was reacted at 80°C for 6 hours, and the time when the NCO content became 0.1% or less was regarded as At the end of the reaction, the urethane acrylate of the present invention is obtained.

Its average molecular weight (Mw = 4500, Mn = 1500), viscosity 6Pa · s (60 ℃).

In addition, the components of the obtained urethane acrylate were confirmed by HPLC and GPC, and it was found that the content of urethane acrylate was 64% (ratio to the total amount), and the urethane acrylate that was not urethanized The content of acrylates (unreacted DPEThexaA and acrylates of by-produced pentaerythritol polymers, etc.) was 36%.

Embodiment B (synthetic example 2)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulator, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 of the raw material (hydroxyl value: 92mg KOH/g, hydroxyl equivalent: 609.9g/ 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 urethane reaction catalyst, and stirred until uniform, so that the internal temperature was 50°C . Next, 60.59 g (0.36 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80°C, and after the addition, it was reacted at 80°C for 6 hours, and the time when the NCO content became 0.1% or less was regarded as At the end of the reaction, the urethane acrylate of the present invention is obtained.

Its average molecular weight (Mw=5500, Mn=1800), viscosity 11Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 74% (ratio to the total amount), and the content of the non-urethane acrylate was 26%.

Embodiment C (synthesis example 3)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device, add a mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA, and TPETA (hydroxyl value: 120 mg KOH/g, hydroxyl equivalent: 467.6 g/Eq) 423.78g (0.91mol), 0.25g of 4-methoxyphenol as a polymerization inhibitor, 0.25g of dibutyltin dilaurate as a urethanization reaction catalyst and stir until uniform, so that the internal temperature is 50°C. Next, 76.22 g (0.45 moles) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80°C, and after the addition, it was reacted at 80°C for 6 hours, and the time when the NCO content became 0.1% or less was regarded as At the end of the reaction, the urethane acrylate of the present invention is obtained.

Its average molecular weight (Mw=7800, Mn=1700) and viscosity is 16Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 73% (ratio to the total amount), and the content of the non-urethane acrylate was 27%.

Embodiment D (synthetic example 4)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulator, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 of the raw material (hydroxyl value: 92mg KOH/g, hydroxyl equivalent: 609.9g/ 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, dilauric acid as a urethane reaction catalyst 0.20 g of dibutyltin and stir until uniform, so that the internal temperature is 50°C. Next, 5.83 g (0.33 moles) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80°C, and after the addition, it was reacted at 80°C for 6 hours, and the time when the NCO content became 0.1% or less was regarded as end point of the reaction. It heated to 60 degreeC, the solvent (2-butanone) was distilled off under reduced pressure, and the urethane acrylate of this invention was obtained.

Its average molecular weight (Mw=10300, Mn=1800) and viscosity is 18Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 74% (ratio to the total amount), and the content of the non-urethane acrylate was 26%.

Embodiment E (synthetic example 5)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulator, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 of the raw material (hydroxyl value: 92mg KOH/g, hydroxyl equivalent: 609.9g/ Eq) 308.78g (0.51mol), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixing ratio by weight: 70/30, hydroxyl equivalent: 421.9g/Eq) 29.06g (0.07mol), glycerin 4.23g (0.05 mol), 100.00g of 2-butanone, 0.20g of 4-methoxyphenol as a polymerization inhibitor, 0.20g of dibutyltin dilaurate as a urethanization reaction catalyst and stir until uniform, so that the internal temperature is 50 ℃. Next, 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, it was reacted at 80°C for 6 hours, and the time when the NCO content became 0.1% or less was regarded as end point of the reaction. It heated to 60 degreeC, the solvent (2-butanone) was distilled off under reduced pressure, and the urethane acrylate of this invention was obtained.

Its average molecular weight (Mw=11300, Mn=1700) and viscosity is 17Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 74% (ratio to the total amount), and the content of the non-urethane acrylate was 26%.

Embodiment F (synthesis example 6)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulator, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 of the raw material (hydroxyl value: 92mg KOH/g, hydroxyl equivalent: 609.9g/ Eq) 325.95g (0.53mol), 8.44g (0.07mol) of 2-hydroxyethyl acrylate, 4.46g (0.05mol) of glycerin, 100.00g of 2-butanone, 0.20g of 4-methoxyphenol as a polymerization inhibitor . 0.20 g of dibutyltin dilaurate as a urethanization reaction catalyst was stirred until uniform, and the internal temperature was set to 50°C. Next, 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, it was reacted at 80°C for 6 hours, and the time when the NCO content became 0.1% or less was regarded as end point of the reaction. It heated to 60 degreeC, the solvent (2-butanone) was distilled off under reduced pressure, and the urethane acrylate of this invention was obtained.

Its average molecular weight (Mw=9500, Mn=1800) and viscosity is 17Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 74% (ratio to the total amount), and the content of the non-urethane acrylate was 26%.

Embodiment G (synthesis example 7)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulator, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 of the raw material (hydroxyl value: 92mg KOH/g, hydroxyl equivalent: 609.9g/ Eq) 320.42g (0.53mol), 8.94g (0.08mol) of 2-hydroxyethyl acrylate, 5.91g (0.06mol) of glycerin, 100.00g of 2-butanone, 0.20g of 4-methoxyphenol as a polymerization inhibitor . 0.20 g of dibutyltin dilaurate as a urethanization reaction catalyst was stirred until uniform, and the internal temperature was set to 50°C. Next, 64.73 g (0.38 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80°C, and after the addition, it was reacted at 80°C for 6 hours, and the time when the NCO content became 0.1% or less was regarded as end point of the reaction. It heated to 60 degreeC, the solvent (2-butanone) was distilled off under reduced pressure, and the urethane acrylate of this invention was obtained.

Its average molecular weight (Mw=19700, Mn=1800) and viscosity is 27Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 75% (ratio to the total amount), and the content of the non-urethane acrylate was 25%.

Embodiment H (synthesis example 8)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulator, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 of the raw material (hydroxyl value: 92mg KOH/g, hydroxyl equivalent: 609.9g/ Eq) 330.55g (0.54mol), 2-butanone 100.00g, 4-methoxyphenol 0.20g as a polymerization inhibitor, 0.20g dibutyltin dilaurate as a urethane reaction catalyst and stir until uniform , so that the internal temperature is 50°C. Next, 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. The reaction was carried out at 80° C. for 6 hours, and the time when the above-mentioned NCO content became 0.1% or less was regarded as the end point of the reaction. It heated to 60 degreeC, the solvent (2-butanone) was distilled off under reduced pressure, and the urethane acrylate of this invention was obtained.

Its average molecular weight (Mw=16300, Mn=2000) and viscosity is 24Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 74% (ratio to the total amount), and the content of the non-urethane acrylate was 26%.

Embodiment 1 (synthesis example 9)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulator, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 of the raw material (hydroxyl value: 92mg KOH/g, hydroxyl equivalent: 609.9g/ Eq) 337.88g (0.55mol), 2-butanone 100.00g, 4-methoxyphenol 0.20g as a polymerization inhibitor, 0.20g dibutyltin dilaurate as a urethane reaction catalyst and stir until uniform , so that the internal temperature is 50°C. Next, 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. The reaction was carried out at 80° C. for 6 hours, and the time when the above-mentioned NCO content became 0.1% or less was regarded as the end point of the reaction. It heated to 60 degreeC, the solvent (2-butanone) was distilled off under reduced pressure, and the urethane acrylate of this invention was obtained.

Its average molecular weight (Mw=8500, Mn=1800) and viscosity is 12Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 74% (ratio to the total amount), and the content of the non-urethane acrylate was 26%.

Embodiment J (synthesis example 10)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Raw Material Synthesis Example 1 (hydroxyl value: 80mg KOH/g, hydroxyl equivalent: 701.4g/ Eq) 331.80g (0.54mol), 100.00g of 2-butanone, 0.20g of 4-methoxyphenol as a polymerization inhibitor, 0.20g of dibutyltin dilaurate as a urethanization reaction catalyst and stir until uniform , so that the internal temperature is 50°C. Next, 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. The reaction was carried out at 80° C. for 6 hours, and the time when the above-mentioned NCO content became 0.1% or less was regarded as the end point of the reaction. It heated to 60 degreeC, the solvent (2-butanone) was distilled off under reduced pressure, and the urethane acrylate of this invention was obtained.

Its average molecular weight (Mw=11700, Mn=1800) and viscosity is 23Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 66% (ratio with respect to the total amount), and the content of the non-urethanized acrylate was 34%.

Embodiment K (synthesis example 11)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 3 of raw materials (hydroxyl value: 120mg KOH/g, hydroxyl equivalent: 467.6g/ Eq) 305.74g (0.50mol), 2-butanone 100.00g, 4-methoxyphenol 0.20g as a polymerization inhibitor, 0.20g dibutyltin dilaurate as a urethane reaction catalyst and stir until uniform , so that the internal temperature is 50°C. Next, 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. The reaction was carried out at 80° C. for 6 hours, and the time when the above-mentioned NCO content became 0.1% or less was regarded as the end point of the reaction. It heated to 60 degreeC, the solvent (2-butanone) was distilled off under reduced pressure, and the urethane acrylate of this invention was obtained.

Its average molecular weight (Mw=27700, Mn=2000) and viscosity is 32Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 74% (ratio to the total amount), and the content of the non-urethane acrylate was 26%.

Comparative Synthesis Example 1

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device, a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA (hydroxyl value: 45 mg KOH/g, hydroxyl equivalent: 1246.9 g/Eq) 473.39g (0.38mol), 0.25g of 4-methoxyphenol as a polymerization inhibitor, 0.25g of dibutyltin dilaurate as a urethanization reaction catalyst and stir until uniform, so that the internal temperature is 50°C. Next, 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, it was reacted at 80°C for 6 hours, and the time when the NCO content became 0.1% or less was regarded as At the end of the reaction, urethane acrylate is obtained.

Its average molecular weight (Mw=2200, Mn=1200), viscosity 2Pa·s (60°C).

In addition, in the obtained urethane acrylate, the content of the urethane acrylate was 48% (ratio with respect to the total amount), and the content of the non-urethanized acrylate was 52%.

Comparative Synthesis Example 2

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device, add a mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA, and TPETA obtained in Synthesis Example 2 of raw materials for comparison (hydroxyl value: 140 mg KOH/g, hydroxyl equivalent : 400.8g/Eq) 413.28g (1.03mol), 0.25g of 4-methoxyphenol as a polymerization inhibitor, 0.25g of dibutyltin dilaurate as a urethane reaction catalyst and stir until uniform, so that the inside The temperature is 50°C. Next, 86.72 g (0.52 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80°C, and after the addition, it was reacted at 80°C for 2 hours, gelling occurred, and the target urethane acrylic acid could not be obtained. ester.

Comparative Synthesis Example 3

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulator, add a mixture of DPETtetraA, DPETpentaA, DPEThexaA and TPETA obtained in Synthesis Example 2 of the raw material (hydroxyl value: 92mg KOH/g, hydroxyl equivalent: 609.9g/ 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 and stirred until uniform, so that the internal temperature was 50°C . Next, 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 after the addition, it was reacted at 80°C for 4 hours to cause gelation, The target urethane acrylate could not be obtained.

(comparative synthesis example 4)

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device, add a mixture of DPETtriA, DPETtetraA, DPETpentaA, DPEThexaA, and TPETA (hydroxyl value: 120 mg KOH/g, hydroxyl equivalent: 467.6 g/Eq) 297.93g (0.49mol), 0.25g of 4-methoxyphenol as a polymerization inhibitor, 0.25g of dibutyltin dilaurate as a urethanization reaction catalyst and stir until uniform, so that the internal temperature is 50°C. Next, 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 after the addition, it was reacted at 80°C for 2 hours to cause gelation, The target urethane acrylate could not be obtained.

Examples 1-4 and Comparative Examples 1-2

Each component was formulated in the composition shown in Table 1, and mixed until uniform, and the resin composition of this invention and the resin composition of the comparative example were manufactured. Each of the obtained resin compositions was coated on a PET film (film thickness 125 μm) after an easy-adhesive treatment with a bar coater, and dried at about 80°C to about 100°C. Each of the obtained coating films was irradiated with ultraviolet rays by an ultraviolet irradiator (JAPANSTORAGE BATTERY CO, LTD.: CS 30L-1-1) to cure the coating films. A PET film (hard coat film) having a hard coat layer having a film thickness of about 5 μm was obtained.

In addition, 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 ).

In addition, the unit of the numerical value in Table 1 is "mass part".

Table 1

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative example 2 The compound of synthetic example 1 50 The compound of synthetic example 2 50 40 The compound of synthetic example 3 50 The compound of comparative synthesis example 1 50 DPHA*1 10 50 MEK*2 50 50 50 50 50 50 Irg.184*3 5 5 5 5 5 5

(Note)

^* 1.DPHA: dipentaerythritol pentaacrylate/hexaacrylate mixture

^* 2.MEK: methyl ethyl ketone

^* 3.Irg.184: Ciba Specialty Chemicals Co., Ltd., 1-hydroxycyclohexyl phenyl ketone

Table 2 shows the results of evaluating the following items about the hard coat films obtained in Examples 1-4 and Comparative Examples 1-2.

(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 with the cured film to be measured, a pencil is applied at an angle of 45 degrees, and a load of 750g is applied from above to scratch about 5mm, and the pencil that does not cause scratches 4 or more times out of 5 times hardness representation.

(adhesion)

The surface of the obtained hard-coat film after the optical rotation resistance test was scratched with a knife (30 mm on one side), and a cellophane tape was stuck thereon, and peeled off at an angle of 90 degrees.

○: No peeling

×: Peeling occurs

(scratch 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 scratches was visually checked.

○: No scratches

×: Scratches occur

(curly)

The obtained hard coat film was cut into 5 cm x 5 cm, placed in a drying oven at 80° C. for 1 hour, and then returned to room temperature. Measure the respective heights of the four raised sides on a horizontal platform, and take the sum of the four sides as the measured value (unit: mm). At this time, the curl of the substrate itself was 0 mm.

(Exterior)

The state of cracking, whitening, haze, etc. on the surface was judged with the naked eye.

Evaluation ○: good

×: Obvious cracking occurs

Table 2

Pencil hardness Adhesion Scratch resistance curly Exterior Example 1 3H ○ ○ 20 ○ Example 2 3H ○ ○ 19 ○ Example 3 3H ○ ○ 17 ○ Example 4 3H ○ ○ twenty one ○ Comparative example 1 3H ○ ○ 25 ○ Comparative example 2 3H ○ ○ 35 ○

From the results in Table 2, it is clear that the film having the cured film obtained by curing the resin composition of the present invention has good hardness, adhesion, and scratch resistance, no cracks, and less curling than the comparative example. Small.

Embodiment 5～7 and comparative example 3

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

The thickness of each obtained cured film was about 200 μm. This cured film was peeled off from the stainless steel plate to obtain a cured film for testing.

In addition, 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 ).

In addition, the unit of the numerical value in Table 3 is "mass part".

table 3

Example 5 Example 6 Example 7 Comparative example 3 Compound of Synthesis Example 1 80 Compound of Synthesis Example 2 80 Compound of Synthesis Example 3 80 Comparing the compound of Synthesis Example 1 80 HDDA*4 20 20 20 20 Irg.184 3 3 3 3

(Note)

^* 4.HDDA: 1,6-hexanediol diacrylate

(Stretching test)

In accordance with JIS K 7162, dumbbell-shaped test pieces were produced from the films obtained in Examples 5 to 7 and Comparative Example 3, 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: Stress at the breaking point

3: Elongation at breaking point

Table 4

Young's modulus (MPa) Burst point stress (MPa) Elongation at breaking point (%) Example 5 1050 13.8 1.5 Example 6 1070 15.2 1.8 Example 7 1060 17.9 2.1 Comparative example 3 1020 9.7 1.0

It is clear from the results in Table 4 that the cured film obtained by curing the resin composition of the present invention has a large stress at break point and elongation at break point, and is softer and tougher than the comparative example.

Embodiment 8～15

Each component was mixed with the composition shown in following Table 5, and it mixed until uniform, and the resin composition of this invention was manufactured. In addition, "MEK" and "Irg.184" in a table have the same meaning as Table 1.

Using each obtained resin composition, it carried out similarly to the said Examples 1-4, and obtained the PET film (hard-coat film) which has a hard-coat layer of film thickness about 5 micrometers.

About the obtained hard coat film, it evaluated similarly to Examples 1-4, and the result is shown in following Table 6.

table 5

Table 6

Pencil hardness Adhesion Scratch resistance curly Exterior Example 8 3H ○ ○ 16 ○ Example 9 3H ○ ○ 17 ○ Example 10 3H ○ ○ 17 ○ Example 11 3H ○ ○ 16 ○ Example 12 3H ○ ○ 16 ○ Example 13 3H ○ ○ 18 ○ Example 14 3H ○ ○ 16 ○ Example 15 3H ○ ○ 15 ○

As is evident from the results in Table 6, the film having the cured coating film obtained by curing the resin composition of the present invention had good hardness, adhesion, and scratch resistance, and no cracks occurred.

The cured film obtained by curing the resin composition of the present invention is characterized in that it has good hardness, adhesion, and scratch resistance, and does not generate cracks, while maintaining the required properties as a hard coat layer and simultaneously It has the characteristics of small curl, softness and toughness.

Industrial applicability

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 a plastic film or a hard coat layer of a small case, a color filter, a black matrix, and a spacer.

Claims (19)

1. a carbamate (methyl) acrylic compound (A), it obtains by making any one polyisocyanates (b) comprising diisocyanate cpd with (II) in (I) following (i), (ii) or (iii) react:

I () comprises in the group being selected from and being made up of Dipentaerythritol three (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate at least two kinds and hydroxyl value is Dipentaerythritol many (methyl) acrylate mixture (a) (hereinafter referred to as this mixture (a)) of 80 ~ 120mg KOH/g; Or

(ii) this mixture (a) and glycerine; Or

(iii) (methyl) acrylate three of this mixture (a), glycerine and C2 ~ C5 aliphatic polybasic (2 ~ 4) alcohol.

2. carbamate (methyl) acrylic compound (A) as claimed in claim 1, wherein, (I) is (i) this mixture (a).

3. carbamate (methyl) acrylic compound (A) as claimed in claim 1, wherein, (II) polyisocyanates (b) for diisocyanate cpd separately or the combinationally using of diisocyanate cpd and tri-isocyanate compound, the ratio of diisocyanate cpd and tri-isocyanate compound is relative to diisocyanate cpd 1 mole, and tri-isocyanate compound is the ratio of 0 ~ 10 mole.

4. carbamate (methyl) acrylic compound (A) as claimed in claim 1, it represents with following general formula (1):

In formula, X is isocyanate residue, and n is the integer of 0 ~ 100,

Y is the organic group that represents with following general formula (2), and a, b and c in formula are respectively the integer of 1≤a≤4,0≤b≤3 and 0≤c≤3, and a+b+c=4,

Further,

A is the organic group that represents with above-mentioned general formula (2), and the X in formula is isocyanate residue, c be 0, a and b be the integer of 1≤a≤5,0≤b≤4, and a+b=5,

B is the organic group that represents with above-mentioned general formula (2), and the X in formula is isocyanate residue, c be 0, a and b be following (i) or (ii):

When () B is present in end i, a and b is the integer of 1≤a≤5,0≤b≤4, and a+b=5,

(ii), when B is present in beyond end, a and b in formula is the integer of 1≤a≤4,0≤b≤3, and a+b=4.

5. the manufacture method of carbamate according to claim 1 (methyl) acrylic compound (A), wherein, with relative to active hydrogen base 1 equivalent in this mixture (a), isocyanate group equivalent in polyisocyanates (b) is the ratio of 0.1 ~ 50 equivalent, and (i) this mixture (a) of (I) and (II) polyisocyanates (b) are reacted.

6. carbamate (methyl) acrylic compound (A) as claimed in claim 1, wherein, (I) is (ii) this mixture (a) and glycerine.

7. the manufacture method of a carbamate (methyl) acrylic compound (A), wherein, with relative to active hydrogen base 1 equivalent in this mixture (a), the ratio that active hydrogen base equivalent in glycerine is 0.01 ~ 10 equivalent, isocyanate group equivalent in (II) polyisocyanates (b) is 0.1 ~ 50 equivalent, makes (II) polyisocyanates (b) in this mixture (a) in claim 1 and glycerine and claim 1 react.

8. a resin combination, it comprises carbamate according to claim 1 (methyl) acrylic compound (A), (methyl) acrylate (B) and Photoepolymerizationinitiater initiater (C).

9. resin combination as claimed in claim 8, it is for hard coat.

10. carbamate (methyl) acrylic compound (A) as claimed in claim 1, wherein, (I) is (methyl) acrylate three of (iii) this mixture (a), glycerine and C2 ~ C5 aliphatic polybasic (2 ~ 4) alcohol.

The manufacture method of 11. carbamate according to claim 1 (methyl) acrylic compound (A), wherein, with relative to active hydrogen base 1 equivalent in this mixture (a), the active hydrogen base equivalent of glycerine is 0.01 ~ 10 equivalent, the active hydrogen base equivalent of (methyl) acrylate of C2 ~ C5 aliphatic polybasic (2 ~ 4) alcohol is 0.01 ~ 10 equivalent, the isocyanate group equivalent of polyisocyanates (b) is the ratio of 0.1 ~ 50 equivalent, make (iii) this mixture (a) of (I) in claim 1, (II) polyisocyanates (b) in (methyl) acrylate three of glycerine and C2 ~ C5 aliphatic polybasic (2 ~ 4) alcohol and claim 1 reacts.

12. carbamates (methyl) acrylic compound (A) as claimed in claim 1, wherein, in the area ratio of high performance liquid chromatography (HPLC) (%), relative to the total amount of this mixture (a), (I) this mixture (a) in comprises 35 ~ 60% Dipentaerythritol five (methyl) acrylate, in addition after adding Dipentaerythritol four (methyl) acrylate and Dipentaerythritol six (methyl) acrylate, three's adds up to 90 ~ 100%, all the other 0 ~ 10% are (methyl) acrylate of more than Dipentaerythritol three (methyl) acrylate and tripentaerythritol polymer.

13. carbamate (methyl) acrylic compound (A) as described in claim 1 or 12, wherein, polyisocyanates (b) for diisocyanate cpd independent.

14. carbamate (methyl) acrylic compound (A) as described in claim 1 or 12, wherein, what polyisocyanates (b) was diisocyanate cpd and tri-isocyanate compound combinationally uses.

15. carbamates (methyl) acrylic compound (A) as claimed in claim 13, wherein, diisocyanate cpd is hexamethylene diisocyanate.

16. carbamates (methyl) acrylic compound (A) as claimed in claim 1, wherein, this mixture (a) is Dipentaerythritol tetraacrylate, the mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate three, or be Dipentaerythritol triacrylate, Dipentaerythritol tetraacrylate, the mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate, polyisocyanates (b) for hexamethylene diisocyanate independent, or hexamethylene diisocyanate and hexamethylene diisocyanate trimer.

17. 1 kinds of resin combinations, it comprises carbamate according to claim 1 (methyl) acrylic compound (A) and Photoepolymerizationinitiater initiater (C).

The cured film of 18. 1 kinds of resin combinations, it comprises carbamate according to claim 1 (methyl) acrylic compound (A) and Photoepolymerizationinitiater initiater (C).

19. carbamates (methyl) acrylic compound (A) as claimed in claim 1, wherein, the viscosity at 60 DEG C is 5 ~ 40Pas.