JP2009235119A - Polymerizable composition, cured product thereof, method for producing cured product, and hard-coated goods - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition forming a hard coat layer which is as thin as several ten nm to several μm, a cured product thereof, a method for producing such a cured product, and hard-coated goods. <P>SOLUTION: The polymerizable composition contains a compound represented by general formula (I) or general formula (II). In the formulae, Q<SB>1</SB>is a group represented by CN or COX<SB>2</SB>, X<SB>2</SB>represents a hydroxy group, a substituted oxy group, a substituted thio group, an amino group, a substituted amino group, a heterocyclic group (provided that it links through a heteroatom) or a halogen atom; X<SB>1</SB>represents a substituted oxy group, a substituted amino group, a heterocyclic group (provided that it links through a heteroatom) or a halogen atom; Z<SB>1</SB>or Z<SB>2</SB>is a linking group in which a linking atom is a heteroatom and which contains a divalent group represented by general formula (III) as a partial structure; Ra, Rb, Rc and Rd each independently represents a hydrogen atom, a halogen atom, a cyano group or an organic residue, Ra and Rb, X<SB>1</SB>and Ra or Rb, and Q<SB>1</SB>and Ra or Rb may bond to each other to form a cyclic structure; and n represents an integer of 2-6. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymerizable composition, a cured product thereof, a method for producing a cured product, and a hard coat article. In particular, the present invention relates to a polymerizable composition capable of forming a thin film hard coat having a thickness of several tens of nanometers to several micrometers even in the presence of oxygen such as in the atmosphere, a cured product obtained by curing the same, and a hard-coated article. It relates to a material suitably used as a coating material, a paint, and various molding materials.

  Currently, plastic materials are used in large quantities in many industries, including the automobile and consumer electronics industries. The reason why a large amount of plastic material is used in this way is because it is light and inexpensive, has transparency such as optical characteristics, and has excellent workability. However, since these plastic materials are softer than glass or metal, they have a drawback that the surface is easily damaged. Therefore, an attempt has been made to improve the wear resistance, scratch resistance, and surface hardness by applying a hard coat treatment to the surface of the plastic material.

  When performing hard coat treatment on plastic materials, it is desirable to reduce the thickness of the hard coat layer to several tens of nanometers to several μm in order to improve the scratch resistance of the surface without impairing the excellent mechanical properties of the plastic materials. . The hard coat layer generally tends to be hard but brittle. When the thickness is thick, mechanical properties such as impact resistance of the hard-coated plastic material are impaired.

  Therefore, attempts have been made to thin the hard coat layer to about several tens of nm to several μm, but the widely used acrylate / methacrylate hard coat materials are easily affected by dissolved oxygen during curing, Since the thin film curing is greatly affected by oxygen, there is a big problem in curing in the atmosphere. For such influence of oxygen, a method of replacing the atmosphere with an inert gas, a method of curing after providing an oxygen blocking layer on the upper layer, a method of using a cationic polymerization hard coat material, and the like have been proposed.

  The method of replacing the atmosphere with an inert gas has a problem that the maintenance cost is enormous because it is necessary to replace the entire facility with an inert gas for curing a wide film or a large molded article. The method of providing an oxygen barrier layer on the upper layer greatly restricts its use because it affects the performance of the resulting hard coat article, for example, the surface hardness decreases. And cationic polymerization type hard coat materials using epoxy materials etc. are very susceptible to moisture, and it is necessary to strictly control the humidity at the manufacturing site, and the maintenance cost is higher than the method using inert gas. Necessary.

  In view of the above situation, the present invention provides a polymerizable composition capable of forming a thin hard coat layer of several tens of nm to several μm even in an oxygen atmosphere such as the atmosphere, a cured product thereof, a curing method, and a hard coat. The purpose is to provide the goods.

As a result of intensive studies to solve these drawbacks, the present inventors have found that the above object can be achieved by using a specific polymerizable compound, and have completed the present invention. The above object of the present invention has been solved by the following means.
<1> A polymerizable composition comprising a compound represented by the following general formula (I) or general formula (II).

(In the general formula, Q ₁ is a group represented by CN or COX ₂ , and X ₂ is a hydroxy group, a substituted oxy group, a substituted thio group, an amino group, a substituted amino group, a heterocyclic group (however, a heteroatom X ₁ represents a substituted oxy group, a substituted amino group, a heterocyclic group (provided that they are connected by a hetero atom) or a halogen atom, and Z ₁ or Z ₂ represents The linking atom is a heteroatom and includes a divalent group represented by the following general formula (III) as a partial structure: Ra, Rb, Rc, and Rd are each independently a hydrogen atom, halogen, Represents an atom, a cyano group, or an organic residue, and Ra and Rb, X ₁ and Ra or Rb, Q ₁ and Ra or Rb may combine with each other to form a cyclic structure, and n is 2 to 6 Represents an integer.)

<2> The polymerizable composition according to <1>, further comprising a thiol compound having at least one SH group.
<3> The polymerizable composition as described in <2>, wherein the thiol compound is a thiol compound having two or more SH groups.
<4> The polymerizable composition as described in <2> or <3>, containing 1% by mass to 25% by mass of the thiol compound.
<5> The polymerizable composition according to any one of <1> to <4>, further comprising a polymerization initiator.
<6> The polymerizable composition as described in <5>, wherein the polymerization initiator is a photopolymerization initiator and is contained in an amount of 0.1% by mass to 15% by mass.
<7> The polymerizable composition according to any one of <1> to <6>, further comprising an inorganic filler.
<8> The polymerizable composition according to <7>, wherein the inorganic filler is contained in an amount of 0.5% by mass to 80% by mass.
<9> A cured product obtained by curing the polymerizable composition according to any one of <1> to <8>.
<10> A method for producing a cured product, wherein the polymerizable composition according to any one of <1> to <8> is cured by irradiation with light having a wavelength of 250 nm to 800 nm.
<11> A hard coat article comprising the cured product of <9> on its surface.

  According to the present invention, a hard coat layer as thin as several tens of nm to several μm can be provided even in an oxygen atmosphere such as the air.

  Hereinafter, the present invention will be described in more detail.

[Polymerizable compound]
The polymerizable composition of the present invention contains a compound having a structure represented by general formula (I) or general formula (II). The structure represented by the general formula (I) or the general formula (II) may be a monovalent or divalent or higher substituent, and Ra, Rb in the general formula (I) or the general formula (II), Rc, Rd, X ₁ and X ₂ may all represent a terminal group and form one compound by itself. When the structure represented by the general formula (I) or the general formula (II) is a monovalent or divalent or higher substituent, Ra, Rb, Rc in the general formula (I) or the general formula (II) , Rd, X ₁ , and X ₂ each have one or more bonds. Further, X ₁ and X ₂ may be a linking group having n connectable sites, and n groups represented by general formula (I) or general formula (II) may be connected to the terminal thereof. (N is an integer of 2 or more) (multimer). Further, at least one of X ₁ and X ₂ may be bonded to the polymer chain. That is, the polymer chain may take a form in which the structure represented by the general formula (I) or the general formula (II) exists in the side chain.

In the general formula (II), Q ₁ is a group represented by CN or COX ₂ . These can be appropriately selected as necessary. In the general formula (II), n is an integer of 2 to 6, and Q ₁ is not limited to CN or COX ₂ alone, and CN and COX ₂ may be used in combination. In that case, the combination of each CN group or COX ₂ group is arbitrary.

Here, examples of the polymer chain include a linear organic polymer as described below. Specific examples include vinyl polymers such as polyurethane, novolac, and polyvinyl alcohol, polyhydroxystyrene, polystyrene, poly (meth) acrylic acid ester, poly (meth) acrylic acid amide, and polyacetal. These polymers may be homopolymers or copolymers (copolymers). In the general formula (I) or the general formula (II), X ₁ and X ₂ represent a hetero atom or a halogen atom, but they may be a terminal group or a linking group, and other substituents (As mentioned above, the substituent may be linked to the structure of general formula (I) or general formula (II) and the polymer chain as described above). The heteroatom is preferably a nonmetallic atom, and specifically includes an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom.

Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. X ₁ is preferably a halogen atom or a group in which X ₁ is a linking group to which another substituent is linked, such as a hydroxyl group, a substituted oxy group, a mercapto group, a substituted thio group, an amino group, or a substituted amino group. Represents a group, a sulfo group, a sulfonato group, a substituted sulfinyl group, a substituted sulfonyl group, a phosphono group, a substituted phosphono group, a phosphonato group, a substituted phosphonato group, a nitro group, or a heterocyclic group (which is linked by a heteroatom). . X ₂ is preferably a halogen atom or a group in which X ₂ is a linking group to which another substituent is linked, such as a hydroxyl group, a substituted oxy group, a mercapto group, a substituted thio group, an amino group, or a substituted amino group. Represents a group or a heterocyclic group (which is linked by a heteroatom).

Ra, Rb, Rc, and Rd each independently represent a hydrogen atom, a halogen atom, a cyano group, or an organic residue. The organic residue is preferably a hydrocarbon group, a substituted oxy group, a substituted thio group, a substituted amino group, a substituted carbonyl group, or a carboxy group that may have a substituent and may contain an unsaturated bond. It is a Lato group. Ra and Rb, _{X 1} and Ra or Rb, _{Q 1} and Ra or Rb may be bonded to each other to form a cyclic structure. n is an integer of 2 to 6, preferably n is an integer of 3 to 6.

Z ₁ or Z ₂ is a linking group containing a divalent group represented by formula (III) as a partial structure, wherein the linking atom is a heteroatom. The n linking heteroatoms of Z ₁ and Z ₂ are any of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom, and preferably in a linked state, a substituted oxy group, a substituted thio group, an amino group, a substituted atom An amino group and a heterocyclic group (however, linked by a hetero atom) are formed. More preferably, Z ₁ or Z ₂ is a linking group having a plurality of general formula (III) structures. Further, n-number of the connecting portion of the _{Z 2} preferably has a further partial structure as a -OCO- group.
The most preferred specific examples of Z ₁ and Z ₂ include the linking group structures described in “Specific Examples” below.

Next, each substituent in X ₁ , X ₂ , Ra, Rb, Rc, and Rd will be described.
Examples of the hydrocarbon group which may have a substituent and may contain an unsaturated bond include an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, and an alkynyl group. And substituted alkynyl groups.

  Examples of the alkyl group include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group , Isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  The substituted alkyl group is composed of a bond between a substituent and an alkylene group, and as the substituent, a monovalent nonmetallic atomic group excluding hydrogen is used. Preferred examples include halogen atoms (—F, —Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-ali Rucarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′- Dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl- N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl- N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-al Luureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxy Carbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N- Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group (hereinafter referred to as carboxylate),

Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N - acylsulfamoyl group and a conjugate base group, N- alkylsulfonylsulfamoyl group _{(-SO 2 NHSO 2 (alkyl)} ) and its conjugated base group, N- aryl sulfonylsulfamoyl group _(-SO 2 NHSO ₂ (Allyl)) and its conjugate base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ (alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (allyl)) and its conjugate base group, An alkoxysilyl group (—Si (O-alkyl) ₃ ),

Aryloxysilyl group (—Si (O-allyl) ₃ ), hydroxysilyl group (—Si (OH) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter, phosphonate) Group), a dialkylphosphono group (—PO ₃ (alkyl) ₂ ), a diarylphosphono group (—PO ₃ (aryl) ₂ ), an alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), Monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group ( hereinafter referred to as aryl phosphite Hona preparative group), phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonatooxy group), di Le Kill phosphono group _{(-OPO 3 (alkyl) 2)} , diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl Phosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (Hereinafter referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, and alkynyl group.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl Group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylcarbamoyl group Group, a phenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group include phosphono phenyl group, and the like phosphonium Hona preparative phenyl group. Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group, phenylethynyl group and the like.

The above-described acyl group (R _{4 CO-),} R 4 is a hydrogen atom and the above alkyl group, aryl group, alkenyl group, and an alkynyl group. On the other hand, examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched alkylene groups having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

  Specific examples of preferred substituted alkyl groups include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, Ruthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N- Methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonyl Bonirumechiru group, butoxycarbonyl methyl group, allyloxycarbonyl methyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenyl methyl group,

Trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N -Methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N -Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobu Group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1 -Phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. can be mentioned.

  Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, naphthyl Group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, and fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  The substituted aryl group is a group in which the substituent is bonded to the aryl group, and those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group described above are used. Examples of preferred substituents include the above-described alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of these substituted aryl groups include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, Hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, phenylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetyl Oxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoyl Minofeniru group,

Carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl Group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophene Group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

  Examples of the alkenyl group include those described above. The substituted alkenyl group is a group in which the substituent is replaced and bonded to a hydrogen atom of the alkenyl group, and as the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkenyl group uses the above-mentioned alkenyl group. Can do.

  Examples of the alkynyl group include those described above. The substituted alkynyl group is a group in which the substituent is replaced with a hydrogen atom of the alkynyl group, and the substituent in the above-described substituted alkyl group is used as this substituent, while the alkynyl group uses the above-described alkynyl group. be able to.

  Examples of the compound represented by the general formula (I) or the general formula (II) of the present invention are shown below, but the present invention is not limited to these compounds.

[Thiol compound]
The polymerizable composition of the present invention preferably contains a thiol compound.
The thiol compound that can be used in the polymerizable composition of the present invention is not particularly limited as long as it is a compound having one or more mercapto groups in the molecule. Preferably, a polyfunctional thiol having two or more SH groups is more preferable because the obtained cured product is excellent in scratch resistance.

  Specific examples of the thiol compound include, for example, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, methyl mercaptopropionate, octyl mercaptopropionate, methoxybutyl mercaptopropionate, tridecyl mercaptopropionate, thioglycolic acid, thiol Ammonium glycolate, monoethanolamine thioglycolate, sodium thioglycolate, methyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, Monofunctional thiol compounds such as 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,2-cyclohexanedithiol, decanedithiol, ethylene glycol bis Thioglycolate, ethylene glycol bisthiopropionate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, pentaerythritol Tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, dipentaerythritol hexathiopropionate, other esters of polyhydric alcohol and mercaptopropionic acid, trimer Ptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto And polyfunctional thiol compounds such as -s-triazine. These thiol monomers may be used alone or in combination of two or more.

  The preferred blending amount when using the thiol compound is excellent in both the curability in the air and the surface hardness of the resulting cured product, and is more preferably 1% by mass to 25% by mass in the polymerizable composition. Is 3% by mass to 20% by mass, more preferably 5% by mass to 15% by mass.

[Polymerization initiator]
The polymerizable composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
The polymerizable composition of the present invention can be cured by light irradiation or heating in the presence of a photopolymerization initiator or a thermal polymerization initiator. In forming the cured product, a photopolymerization initiator and a thermal initiator can be used in combination.

  First, the photopolymerization initiator that can be used in the present invention will be described. Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A No. 2001-139663, etc.), 2,3- Examples include dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins.

  Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is. Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

  Examples of the borate salt are described in, for example, Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, MartIn “Rad Tech'98. ProceedIng AprIl pages 19-22, 1998, ChIcago”. Organic borates to be mentioned are the compounds described. For example, the compounds described in JP-A-2002-116539, paragraph numbers [0022] to [0027] can be mentioned. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

  Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like. Specifically, Examples 1 to 21 described in JP-A 2000-80068 are particularly preferable.

  Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

  Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M.M. P. Examples include compounds described in Hutt “Jurnal of Heterocyclic Ic ChemIstry”, Vol. 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds, such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl). -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl) Acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, p.14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.

  Examples of inorganic complexes include bis (η 5 -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.

Examples of coumarins include 3-ketocoumarin.
These initiators may be used alone or in combination.

  In addition, “Latest UV Curing Technology”, Technical Information Association, 1991, p. 159, and “UV curing system”, Kiyomi Kato, 1989, General Technology Center, p. Various examples are also described in 65-148 and are useful in the present invention.

  Commercially available photopolymerization initiators include KAYACURE (DETX-S, BP-100, BDDK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, MCA manufactured by Nippon Kayaku Co., Ltd. Irgacure (651, 184, 500, 819, 907, 369, 1173, 1870, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals Co., Ltd., Esacure (KIP100F, KB1, EB3) manufactured by Sartomer , BP, X33, KT046, KT37, KIP150, TZT) and the like, and combinations thereof are preferable examples.

  These photopolymerization initiators are preferably used in the polymerizable composition of the present invention in the range of 0.1% by mass to 15% by mass, more preferably in the range of 1% by mass to 10% by mass. .

  In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination. Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.

  As the thermal polymerization initiator that can be used in the present invention, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used. Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile) as azo compounds such as ammonium sulfate and potassium persulfate And diazoaminobenzene, p-nitrobenzenediazonium and the like.

  Although the preferable usage amount when using these thermal polymerization initiators differs depending on each initiator to be blended, it cannot be generally stated, but is 0.1% by mass to 10% by mass in the polymerizable composition. More preferably, it is 0.3 mass%-8 mass%, More preferably, it is 0.5 mass%-5 mass%. When it is in these ranges, the surface hardness of the obtained cured product becomes excellent.

[Inorganic filler]
In the polymerizable composition of the present invention, various inorganic fillers are preferably used in combination for the purpose of further improving the surface hardness and improving other optical properties such as reflectance and scattering properties.

As an inorganic filler that can be used, an oxide of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony, specific examples include ZrO ₂ , TiO ₂ , and Al _2. Examples include O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , and ITO. In addition, BaSO ₄ , CaCO ₃ , talc and kaolin are included.

  The shape of the inorganic filler used in the present invention is not particularly limited. However, since it is difficult for anisotropy to occur in the mechanical properties and optical properties of the cured product, the shape is preferably spherical rather than needle-like or plate-like. When the inorganic filler is spherical, the particle size is preferably as fine as possible in the dispersion medium, and the mass average particle size is 1 nm to 200 nm, preferably 5 nm to 150 nm, more preferably 10 nm to 100 nm, Particularly preferably, it is 10 nm to 80 nm. By miniaturizing the inorganic filler to 100 nm or less, a cured product that does not impair the transparency can be formed. The particle diameter of the inorganic filler can be measured by a light scattering method or an electron micrograph.

The specific surface area of the inorganic filler ^is preferably 10m ² / g~400m 2 / ^g, it is still more preferably ^{20m 2 / g~200m 2 / g,} 30m 2 / g~150m 2 / g Is most preferred.

  The inorganic filler used in the present invention is preferably added to the coating solution for the layer used as a dispersion in the dispersion medium.

As the dispersion medium for the inorganic filler, it is preferable to use a liquid having a boiling point of 60 ° C to 170 ° C.
Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methyl) Carboxymethyl-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred. Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The inorganic filler is dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

For the purpose of increasing the refractive index of the layer constituting the present invention, it is preferable to use an inorganic filler having a high refractive index. In particular, ZrO ₂ and TiO _{2 are} preferably used as the inorganic filler in this case from the viewpoint of refractive index. ZrO ₂ is most preferable for increasing the refractive index of the hard coat layer, and TiO ₂ fine particles are most preferable as the particles for the high refractive index layer and the medium refractive index layer. As the TiO ₂ particles, an inorganic filler mainly composed of TiO ₂ containing at least one element selected from cobalt, aluminum, and zirconium is particularly preferable. The main component means a component having the largest content (mass%) among the components constituting the particles.

The particles mainly composed of TiO ₂ in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. Most preferably.
The mass average diameter of primary particles of TiO ₂ as a main component is preferably 1 nm to 200 nm, more preferably 1 nm to 150 nm, still more preferably 1 nm to 100 nm, and particularly preferably 1 nm to 80 nm.

The crystal structure of the particles containing TiO ₂ as a main component is preferably a rutile, rutile / anatase mixed crystal, anatase, or amorphous structure, and particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

By containing at least one element selected from Co (cobalt), Al (aluminum), and Zr (zirconium) in particles containing TiO ₂ as a main component, the photocatalytic activity of TiO ₂ can be suppressed. The weather resistance of the inventive film can be improved.
A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination.

The inorganic filler mainly composed of TiO ₂ of the present invention may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.

  Further, when the composition of the present invention contains an inorganic filler, the surface of the inorganic filler may be treated with a silane coupling agent in order to improve the interaction between the resin component and the inorganic filler. Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanatopropyltrimethoxysilane. These silane compounds may be used alone or in combination of two or more. By using it as a silane coupling agent having such a structure, the sealing agent of the present invention can improve adhesion to a substrate or the like.

  The preferable compounding quantity of these inorganic fillers is 0.5 mass%-80 mass% in a polymeric composition, More preferably, it is 2 mass%-70 mass%, More preferably, it is 10 mass%-60 mass%.

[Other polymerizable monomers and oligomers]
The polymerizable composition of the present invention can be used in combination with other polymerizable monomers and oligomers as necessary. Other polymerizable monomers and oligomers have at least one, more preferably 2 to 6 addition-polymerizable ethylene groups, and ethylenically unsaturated groups having a boiling point of 100 ° C. or higher under normal pressure. A compound is preferred.

  Compounds having at least one addition-polymerizable ethylenically unsaturated group and a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth). Monofunctional acrylates and methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, (Acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth) acrylate after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034 And urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid can be mentioned. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

[Other additives]
In addition, in the composition of the present invention, if necessary, a dispersant or surfactant for uniformly dispersing the inorganic filler, a reactive diluent for adjusting viscosity, a thixotropic agent for adjusting thixotropy, and an antifoaming agent Further, it may contain a leveling agent, a polymerization inhibitor, a fluorine-based or silicone-based antifouling agent for the purpose of preventing dirt, an antistatic agent for preventing electrostatic charge, and other additives.

[Preparation of composition]
Preparation of the polymerizable composition thus obtained is prepared by, for example, using the above-mentioned polymerizable compound, thiol compound, photopolymerization initiator, inorganic filler, and the like, using an appropriate mixing device such as a homomixer. It can be prepared by dissolving in a suitable solvent and mixing.

  Solvents that can be used are not particularly limited, but alcohols such as methanol, ethanol, propanol, and isopropanol, ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, and toluene And aromatic compounds such as xylene, and ethers such as diethyl ether and tetrahydrofuran. The density | concentration shall be 10 mass%-about 80 mass% with respect to total solid content, such as a polymeric compound, a thiol compound, an inorganic filler, a photoinitiator.

[Formation of cured product]
The obtained polymerizable composition is applied to the target substrate surface, preferably heated in an oven or the like to remove the solvent, and then irradiated with an active energy ray of 250 nm to 800 nm, or 50 ° C. to By heat-treating at 150 ° C., the resin component can be polymerized to form a hard coat film.
In the present invention, when curing by ultraviolet irradiation, the generation source of ultraviolet rays is not particularly limited, but a known light source such as a high-pressure mercury lamp, a metal halide lamp, an LED, or a laser can be used.

  Examples of the method for applying the polymerizable composition to the substrate in the present invention include roll coating, gravure coating, knife coating, dip coating, spray coating, spin coating, bar coating, slot coating, curtain coating, and screen printing. It can be applied by a conventional coating method. The film thickness formed at this time is usually about several nm to 100 μm, and preferably several tens nm to 10 μm for the formation of the thin film hard coat layer intended by the present invention. When the thickness is less than several nm, sufficient surface hardness cannot be obtained, and when it is thicker than 100 μm, the mechanical strength of the obtained hard coat article is lowered and cracks are easily generated.

In the present invention, the generation source of the curing ultraviolet ray is not particularly limited, but a known light source such as a high-pressure mercury lamp, a metal halide lamp, an LED, or a laser can be used.
The substrate on which the hard coat composition of the present invention is applied is not particularly limited, but is a plastic film or plate for exteriors whose appearance is impaired by scratches, a liquid crystal display element whose transparency decreases due to scratches, organic It is particularly suitably used in optical applications such as EL element substrates. Examples include ABS resin, acrylic resin, polyethersulfone resin, polycarbonate resin, polyarylate resin, polyester resin, polyolefin resin, epoxy resin, polyimide resin, polyvinyl alcohol resin, polystyrene resin, and the like.

  The hard coat article of the present invention thus obtained includes exterior and interior parts for vehicles, exterior parts for home appliances, personal computer cases, mobile phone cases, displays such as liquid crystals, office supplies, interior parts for exteriors and exterior members. It can be used as furniture, various interior members, accessories, toys, sports equipment, packaging members, leisure goods, and the like.

Examples of the present invention will be described below, but the present invention is not limited thereto.
<Synthesis Example 1> Preparation of polymerizable compound (A-1) In a three-necked flask equipped with a stirrer, a condenser tube, and a dropping funnel, 198 g of thionyl chloride was taken and ice-cooled. 0.5 mL of pyridine was added, and 250 g of cyclohexyl 2- (hydroxymethyl) acrylate (a) was added dropwise over 2 hours while being careful that the temperature of the content liquid did not exceed 15 ° C. Subsequently, after stirring at room temperature for 7 hours, the reaction solution was poured into a beaker containing 450 g of ice, and stirring was further continued for 30 minutes. This was transferred to a separatory funnel and washed four times with 400 mL of water. After adding 100 mL of toluene, it was separated into an Erlenmeyer flask, dried over anhydrous magnesium sulfate, filtered, added with 0.54 g of 4-acetamido TEMPO as a polymerization inhibitor, distilled under reduced pressure (9.1 mmHg, 120 ° C.), 2- ( 157 g (57% yield) of chloromethyl) cyclohexyl acrylate (b) was obtained.

  In a three-necked flask equipped with a stirrer and a dropping funnel, 11.3 g of 2,2'-thiodiglycolic acid (c) was taken, and 150 mL of ethyl acetate was added. Under ice cooling, 15.2 g of triethylamine was added, and then 29.0 g of cyclohexyl 2- (chloromethyl) acrylate (b) was added dropwise over 15 minutes, taking care that the reaction solution did not exceed 10 ° C. Subsequently, after stirring at room temperature for 3 hours, the contents were transferred to a separatory funnel and washed twice with 150 mL of water, twice with 150 mL of saturated aqueous sodium bicarbonate, and once with 150 mL of saturated brine. The oil layer was dried over magnesium sulfate and filtered, and 0.034 g of 4-hydroxy TEMPO was added as a polymerization inhibitor, followed by concentration under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 85: 15) to obtain 30.7 g of a polymerizable compound (A-1) (yield 89%).

¹ H-NMR (DMSO-d6): δ 1.20 to 1.50 (12H), 1.78 (4H), 1.65 (4H), 3.53 (4H), 4.78 (6H), 5 .94 (2H), 6.27 (2H).

<Synthesis Example 2> Preparation of polymerizable compound (A-2)

  In the example described in Synthesis Example 1, the reaction was carried out in the same manner except that cyclohexyl 2- (chloromethyl) acrylate (b) was changed to 18.5 g of methyl 2- (chloromethyl) acrylate (d). Compound (A-2) was obtained.

<Synthesis Example 3> Preparation of polymerizable compound (A-3)

  In the example described in Synthesis Example 1, the reaction was conducted in the same manner except that 2,2′-thiodiglycolic acid (c) used was changed to 15.8 g of (ethylenedithio) 26-acetic acid (e), and a polymerizable compound (A-3) was obtained.

<Synthesis Example 4> Preparation of Polymerizable Compound (A-4) In the example described in Synthesis Example 1, 2,2′-thiodiglycolic acid (c) used was 15.6 g of 2-carboxymethylsulfanyl succinic acid (f). The reaction was conducted in the same manner as described above except that the polymerizable compound (A-4) was obtained.

-Thiol compound (B-1) Butanediol bisthioglycolate (manufactured by Sakai Chemical Co., Ltd.)
(B-2) Pentaerythritol tetrakisthioglycolate (manufactured by Sakai Chemical Co., Ltd.)
(B-3) Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK, trade name: Karenz MT)

Inorganic filler (C-1) colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: MEK-ST)
Others, etc. (D-1) Acryloxypropyltrimethoxysilane (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-5103)
(D-2) Dipentaerythritol hexaacrylate (manufactured by Daicel-Cytec, DPHA)

Photoinitiator (E-1) 2-Hydroxy-2-cyclohexylacetophenone (Ciba Specialty Chemicals, trade name: Irgacure 184)

<Examples 1-10, Comparative Examples 1-3>
The polymerizable compound, thiol compound, inorganic filler, photopolymerization initiator, other additives and the like were prepared in a MEK solvent so as to have a total solid content of 20% by mass and stirred to obtain a liquid composition. The formulation composition is shown in Table 1. The numerical values in the table are mass ratios.

-RT (real time)-IR polymerization rate After apply | coating the said composition on a silicon substrate, it heated at 100 degreeC for 1 minute, the solvent was removed, and the uncured composition film | membrane was obtained. The polymerization rate of each of these samples, the disappearance of monomer double bonds in FT-IR, ^i.e., was measured by following the decrease in absorbance at 1400cm ^-1 ~1430cm -1. The FT-IR apparatus uses NICOLET6700 (manufactured by Thermo Electron Co., Ltd., trade name), and the light source uses EXECARE 3000 (mercury xenon lamp), 365 nm bandpass filter manufactured by HOYA CANDEO OPTRONICS, and the irradiation intensity at 365 nm is 24 mW / cm ^2. The irradiation time was 120 seconds (3.6 J / cm ² ).

  The ultimate polymerization rate after irradiation for 120 seconds in each atmosphere was determined by performing the atmosphere in the RT-IR apparatus in a complete nitrogen atmosphere or in the air.

Pencil hardness A member coated on a silicon substrate cured in the air was measured on a target under a load of 1 kgf in accordance with JIS K5400.

  The obtained results are shown in Table 1.

<Examples 11 to 17>
The composition (MEK solution) prepared in Example 1 was applied to the plastic material (film form) shown in Table 2 and photocured in the same manner as described above to obtain a hard coat film.

  As mentioned above, from the results obtained in Examples 1 to 17, the hard coat compositions of the present invention in Examples 1 to 10 are thin film conditions that are susceptible to oxygen inhibition during polymerization, even under an oxygen atmosphere such as in the air. It hardened | cured easily and the hardness of the obtained film | membrane showed 2H-4H and high pencil hardness. Moreover, the hard coat film | membrane formed on the various plastic resin shown in Table 2 using the polymeric composition of Example 1 also showed high pencil hardness, although there are differences with plastic resin base materials.

  Further, for example, as is clear by comparing Examples 1 and 7 with Example 6, the pencil hardness can be further increased by blending the composition of the present invention with an inorganic filler such as silica.

  In addition, for example, as is clear by comparing Examples 7 to 9 with Examples 1 and 10, the polymerization rate in the atmosphere can be further increased by using a thiol compound in combination. However, when the thiol compound is used in combination, the pencil hardness of the cured product tends to decrease slightly.

  On the other hand, the resin composition using the acrylic resin D-2 that does not contain the polymerizable compound of the present invention of Comparative Examples 1 to 3 has a low polymerization rate in the atmosphere, and the resulting cured product has a low pencil hardness. It was.

Claims (11)

Polymeric composition containing the compound represented by the following general formula (I) or general formula (II).

(In the general formula, Q ₁ is a group represented by CN or COX ₂ , and X ₂ is a hydroxy group, a substituted oxy group, a substituted thio group, an amino group, a substituted amino group, a heterocyclic group (however, a heteroatom X ₁ represents a substituted oxy group, a substituted amino group, a heterocyclic group (provided that they are connected by a hetero atom) or a halogen atom, and Z ₁ or Z ₂ represents The linking atom is a heteroatom and includes a divalent group represented by the following general formula (III) as a partial structure: Ra, Rb, Rc and Rd are each independently a hydrogen atom or a halogen atom. Represents a cyano group or an organic residue, and Ra and Rb, X ₁ and Ra or Rb, Q ₁ and Ra or Rb may be bonded to each other to form a cyclic structure, and n is 2-6. Represents an integer.)
  The polymerizable composition according to claim 1, further comprising a thiol compound having at least one SH group.   The polymerizable composition according to claim 2, wherein the thiol compound is a thiol compound having two or more SH groups.   The polymerizable composition according to claim 2 or 3, wherein the thiol compound is contained in an amount of 1% by mass to 25% by mass.   Furthermore, a polymerization initiator is contained, The polymeric composition of any one of Claims 1-4 characterized by the above-mentioned.   The polymerizable composition according to claim 5, wherein the polymerization initiator is a photopolymerization initiator and is contained in an amount of 0.1% by mass to 15% by mass.   Furthermore, an inorganic filler is contained, The polymeric composition of any one of Claims 1-6 characterized by the above-mentioned.   The polymerizable composition according to claim 7, comprising 0.5% to 80% by mass of the inorganic filler.   Hardened | cured material formed by hardening | curing polymeric composition of any one of Claims 1-8.   The manufacturing method of the hardened | cured material characterized by irradiating the polymerizable composition of any one of Claims 1-8 with the light of the wavelength of 250 nm-800 nm, and hardening | curing it.   A hard-coated article comprising the cured product according to claim 9 disposed on a surface thereof.