JP2001261916A - Resin composite material having common continuous structure and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composite material being improved in its dynamic characteristics as compared with those of a polymer consisting of an active energy beam crosslinked polymerizable compound, some of which is optically transparent, and further excellent in dynamic characteristics as compared with those of the resin composite showing a single glass-transition point. SOLUTION: This resin composite material having a common continuous structure comprises (a) a cross linked polymer of a urethane(meth)acrylate cured material having 2-6 (meth)acryloyl groups in one molecule and (b) >=1 thermoplastic resin selected from the group consisting of a polycarbonate-based polymer, a polyester-based polymer, a phenoxy resin, a vinyl acetate-based polymer, a chlorine-containing polymer, a vinyl acetate-based polymer, a styrene- based polymer, a urethane-based polymer, an unvulcanized rubber and a cellulose derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composite used in various fields as a protective film, a protective film, various coating materials, a sealing material, and the like. The present invention relates to a resin composite having excellent mechanical properties such as impact resistance and abrasion resistance and having optical transparency, and a method for producing the same. More specifically, the resin composite comprises a thermoplastic resin and a crosslinked polymer, and has a bicontinuous microphase-separated structure. The present invention relates to a resin composite and a method for producing the same.

[0002]

2. Description of the Related Art Active energy ray-curable compositions are widely used in paints, sealants, etc. because they cure in a very short time, have high working efficiency, and do not cause environmental pollution due to evaporation of solvents. However, the cured product of the composition is a soft type, and the surface hardness, heat resistance and strength are insufficient, or a hard type, hard and brittle, so that cracks are easily generated. Or belongs to either category,
The toughness was inferior to that of a thermoplastic resin having the same degree of rigidity. In order to improve such a defect, attempts have been made to improve the active energy ray-curable composition by forming the active energy ray-curable composition into a resin composite with a thermoplastic resin.

For example, Japanese Patent Application Laid-Open No. H11-80556 discloses a method of improving bisphenol (meth) acrylate with an acrylic resin, a polysulfone resin, and a polyimide resin. Also, Japanese Patent Application Laid-Open No. 7-3399
No. 1 discloses a resin composite comprising a cured product of a photosensitive composition and a thermoplastic resin, both of which form a pseudo-homogeneous compatible structure, and a method for producing the same. JP-A-7-102175 discloses a resin composite comprising dissolving a photosensitive composition and a thermoplastic resin in a solvent, cooling and phase-separating, and then irradiating light to cure the photosensitive composition. A production method and a resin composite having a bicontinuous or spherical domain structure obtained thereby are disclosed.

A report by the Kawamura Physical and Chemical Research Institute, 1998, describes a method for improving ethylene oxide-modified bisphenol-type acrylate with polycarbonate and a method comprising ethylene oxide-modified bisphenol-type acrylate and polysulfone, both of which form a co-continuous structure. And a method for producing the same.

[0005]

However, in the method described in Japanese Patent Application Laid-Open No. H11-80556, an amide polymerizable compound such as N, N-dimethylacrylamide is used to improve the affinity of the resin. Since the combination is essential, the moisture absorption of the resin changes depending on the atmospheric humidity,
There is a problem that the characteristics change significantly.

Further, since the resin composite described in the above-mentioned Japanese Patent Application Laid-Open No. 7-33991 is a quasi-compatible system, the degree of improvement in the mechanical properties is at most a degree of improvement between the cured product of the photosensitive resin and the thermoplastic resin. It is the degree of the weighted arithmetic mean of the composition of both characteristics, and it cannot be said that the characteristics of the constituent materials were fully utilized. Further, the resin composite described in the publication,
There is also a problem that the surface hardness, which is an important property as a paint, tends to decrease.

Further, the method described in the above-mentioned Japanese Patent Application Laid-Open No. 7-102175 uses a polysulfone resin, which generally has poor affinity for the photosensitive composition, as the thermoplastic resin. However, there is a problem in that it is limited to partially acrylated epoxy resins having good affinity for polysulfone. When other resins are used, an organic solvent is added to form a uniform mixed solution in order to uniformly mix the thermoplastic resin and the photosensitive composition. Micro phase separation is generated by cooling or volatilizing the solvent, and in this state, light is irradiated to rapidly cure the photosensitive resin to fix the phase separation structure. For this reason, the characteristics tend to be greatly degraded due to slight differences in manufacturing conditions, and in addition to lack of manufacturing stability and uniformity of the product, the degree of improvement of the characteristics is also caused due to generation of voids in the obtained resin composite. It was not enough.

Furthermore, the resin composition comprising ethylene oxide-modified bisphenol-type acrylate and polycarbonate described in the report of Kawamura Physical and Chemical Research Institute in 1998 has no bicontinuous structure,
The degree of improvement of the mechanical properties is, at most, the degree of the weighted arithmetic average of the composition of the properties of both the cured product of the ultraviolet curable resin and the polycarbonate, and that the properties of the constituent materials were fully utilized. I could not say. Further, the resin composite composed of ethylene oxide-modified bisphenol type acrylate and polysulfone described in the 1998 report of Kawamura Physical and Chemical Research Institute has a co-continuous structure similar to the present invention. However, polysulfone has poor compatibility with acrylates, and the method described in the report is a very limited method applicable only to a combination of ethylene oxide-modified bisphenol type acrylate and polysulfone. For example, even a propylene oxide-modified bisphenol-type acrylate having a structure very similar to an ethylene oxide-modified bisphenol-type acrylate cannot provide a composite having a bicontinuous structure due to poor compatibility. Of course, the compatibility with the urethane (meth) acrylates of the present invention is poor, and a composite having a bicontinuous structure cannot be obtained. In other words, the energy ray-curable resin whose physical properties can be improved by polysulfone has been limited to ethylene oxide-modified bisphenol type acrylate.

The problem to be solved by the present invention is to provide a resin composite of an active energy ray cross-linked polymer having better mechanical properties than a resin composite exhibiting one glass transition temperature, preferably an optically transparent resin. It is to provide a simple resin composite.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained a uniform mixture of a specific active energy ray-crosslinkable polymerizable compound and a specific thermoplastic resin into an arbitrary shape. It was found that by shaping and curing by irradiation with active energy rays and at the same time causing phase separation, it was possible to stably produce a resin composite with improved mechanical properties, and completed the present invention. .

That is, in order to solve the above-mentioned problems, the present invention provides a copolymer comprising (I) a crosslinked polymer which is a cured product of an active energy ray crosslinkable polymerizable compound, and (b) a thermoplastic resin. A resin composite having a continuous structure, wherein (1) the active energy ray-crosslinkable polymerizable compound is a urethane (meth) acrylate having 2 to 6 (meth) acryloyl groups in one molecule, and (2) Thermoplastic resin, polycarbonate polymer, polyester polymer, phenoxy resin,
Resin composite that is one or more thermoplastic resins selected from the group consisting of vinyl acetal-based polymers, vinyl chloride-based polymers, vinyl acetate-based polymers, styrene-based polymers, urethane-based polymers, uncrosslinked rubbers and cellulose derivatives Provide body.

In order to solve the above-mentioned problems, the present invention provides (II) a resin composite having a bicontinuous structure of 0.02
The present invention provides the resin composite according to the above item (I), which has a thermoplastic resin phase having a network structure having a size in a range of from about 0.1 μm to about 0.1 μm.

In order to solve the above-mentioned problems, the present invention provides (III) a resin composite having a bicontinuous structure having two glass transition temperatures (Tg).
Or, a resin composite according to the item (II) is provided.

In order to solve the above-mentioned problems, the present invention provides a di (urethane) (meth) acrylate, which is a reaction product of 2-hydroxy-3-phenoxypropyl (meth) acrylate and hexamethylene diisocyanate. (Meth) acrylate, wherein the thermoplastic resin is a polyester polymer, a phenoxy resin, a vinyl acetal polymer, a vinyl chloride polymer, a vinyl acetate polymer, a styrene polymer, a urethane polymer, and an uncrosslinked rubber (I) to which are one or more resins selected from the group consisting of
(III) The resin composite according to any one of the above (3) is provided.

Further, in order to solve the above-mentioned problems, the present invention provides (V) urethane (meth) acrylate, which is a reaction product of 2-hydroxy-3-phenoxypropyl (meth) acrylate and tolylene diisocyanate. Meth) acrylate, wherein the thermoplastic resin is a polycarbonate polymer, a polyester polymer, a phenoxy resin, a vinyl acetal polymer, a vinyl chloride polymer,
The resin composite according to any one of the above (I) to (III), which is at least one resin selected from the group consisting of a vinyl acetate polymer, a styrene polymer, a urethane polymer and an uncrosslinked rubber. Provide body.

According to the present invention, in order to solve the above-mentioned problems, the urethane (meth) acrylate (VI) is tetra (meth) acrylate which is a reaction product of glycerol (meth) acrylate and hexamethylene diisocyanate, The plastic resin is a group consisting of a polyester polymer, a phenoxy resin, a vinyl acetal polymer, a vinyl acetate polymer, a vinyl chloride polymer, a styrene polymer, a urethane polymer, an uncrosslinked rubber, and a cellulose derivative. (I) to (I) which are one or more resins selected from
(II) A resin composite according to any one of the above (1).

In order to solve the above-mentioned problems, the present invention provides (VII) a method in which urethane (meth) acrylate is a reaction product of pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate.
Acrylate, the thermoplastic resin is a vinyl acetal polymer, vinyl acetate polymer, styrene polymer,
The resin composite according to any one of the above (I) to (III), which is one or more thermoplastic resins selected from the group consisting of a urethane-based polymer, an uncrosslinked rubber and a cellulose derivative.

According to the present invention, in order to solve the above-mentioned problems, (VIII) the urethane (meth) acrylate is hexa (meth) acrylate which is a reaction product of pentaerythritol tri (meth) acrylate and tolylene diisocyanate. , A thermoplastic resin is a polyester polymer, a vinyl acetal polymer, a vinyl chloride polymer,
(I) to (II), which are one or more thermoplastic resins selected from the group consisting of vinyl acetate polymers, styrene polymers, urethane polymers, uncrosslinked rubbers and cellulose derivatives.
The resin composite according to any one of the item I) is provided.

In order to solve the above-mentioned problems, the present invention provides (IX) (1) an active energy ray-curable urethane (meth) acrylate having 2 to 6 (meth) acryloyl groups in one molecule, and (2) Polycarbonate polymer, polyester polymer, phenoxy resin, vinyl acetal polymer, chlorine-containing vinyl polymer, vinyl acetate polymer, styrene polymer, urethane polymer, uncrosslinked rubber and cellulose After shaping a homogeneous mixture of at least one thermoplastic resin selected from the group consisting of derivatives, the molded article of the homogeneous mixture is cured by irradiating with active energy rays to induce phase separation, The present invention provides a method for producing a resin composite according to the above (I), which fixes a continuous structure.

In order to solve the above-mentioned problems, the present invention provides (X) (1) an active energy ray-curable urethane (meth) acrylate, (2) a thermoplastic resin, and (3) a solvent for dissolving these. After shaping a homogeneous mixed solution consisting of, the solvent is dried and removed to form a shaped article of the homogeneous mixed solution,
The method for producing a resin composite according to the above (IX), which comprises irradiating an active energy ray thereafter, is provided.

In order to solve the above-mentioned problems, the present invention provides the above (IX) or (X), wherein the (XI) homogeneous mixture contains a photopolymerization initiator and the active energy rays are ultraviolet rays. Provided is a method for producing a resin composite.

In order to solve the above problems, the present invention provides (XII) an active energy ray irradiation temperature of 50 to 2;
A method for producing the resin composite according to the above (IX), (X) or (XI), wherein the temperature is 00 ° C.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composite of the present invention comprises a crosslinked polymer which is a cured product of a thermoplastic resin and an active energy ray crosslinkable polymerizable compound (hereinafter referred to as a “cured product of an active energy ray crosslinked polymerizable compound”). The “certain crosslinked polymer” is sometimes referred to as “active energy ray crosslinked polymer”.) The resin composite of the present invention includes a phase having a relatively high thermoplastic resin concentration (hereinafter, referred to as a thermoplastic resin phase) and a phase having a relatively high active energy ray crosslinked polymer concentration (hereinafter, a crosslinked polymer phase). ), Which has a phase-separated structure in which each phase is three-dimensionally continuous, that is, a bicontinuous structure. In a cross section in any direction of the resin composite of the present invention observed with a transmission electron microscope, a thermoplastic resin phase continuous in a network is observed. The mesh may have partially broken portions. Further, even when the resin composite of the present invention is immersed in a solvent that dissolves a thermoplastic resin, the active energy ray crosslinked polymer phase does not decompose into powder.

From these facts, the resin composite of the present invention is characterized in that almost spherical cells composed of the active energy ray crosslinked polymer phase are hardly formed by the thermoplastic resin phase which is a three-dimensional network continuous phase. It is wrapped but not completely wrapped, and it is considered that the cells are connected to each other.

The network size of the thermoplastic resin phase in the resin composite is preferably in the range of 0.01 to 10 μm.
The range of from 02 to 5 μm is particularly preferred. If the network size of the thermoplastic resin phase is less than 0.01 μm, the degree of improvement in mechanical properties tends to be insufficient, and if the network size of the thermoplastic resin phase exceeds 10 μm, the degree of improvement in mechanical properties is reduced. It is not preferable because it tends to be insufficient or rather lower. In order to obtain a resin composite that is optically transparent and has sufficient mechanical properties, the network size of the thermoplastic resin phase in the resin composite is preferably in the range of 0.02 to 0.1 μm. preferable. The network size of the thermoplastic resin phase can be measured with a transmission electron microscope. The mesh size can be determined as an average value of the center-to-center distances of the phases surrounded by the mesh in the electron microscope image.

The resin composite of the present invention has a glass transition temperature TgC of the crosslinked polymer constituting the resin composite and a glass transition temperature TgL of the thermoplastic resin constituting the resin composite, respectively. , Two glass transition temperatures Tg
1 and Tg2 (provided that Tg1 <Tg2). By having two glass transition temperatures, the properties of the crosslinked polymer and the thermoplastic resin constituting the present resin composite can be higher than the weighted arithmetic average of the composition. At this time, TgC <TgL may be satisfied, or TgC> TgL. However, in general, when TgC = TgL (including TgC ≒ TgL), the two glass transition temperatures degenerate, and even in the resin composite according to the present invention, the presence of two Tg may not occur. Cannot be determined. However, even in such a case, two glass transition temperatures may be observed. In addition, in the case of an asymmetric composition having a large difference in the resin composition ratio or in the case where the thermoplastic resin is a crystalline resin, the presence of two glass transition temperatures may not be distinguished.

The glass transition temperature (Tg) can be measured by any measurement method, for example, dynamic viscoelasticity, differential calorimetry (DSC), etc. Is preferred. The measurement frequency and the heating rate of the dynamic viscoelasticity can be arbitrarily set according to the characteristics of the sample. Tg by dynamic viscoelasticity measurement is tan
It is given as a peak in a graph of the temperature dependence of δ (= loss modulus / storage modulus).

Generally, the glass transition temperature Tg of a crosslinked polymer
Tg between C and the glass transition temperature TgL of the thermoplastic resin.
When one is present, the resin composite is (pseudo)
This indicates that the polymer is in a compatible state, and the mechanical properties generally indicate a weighted arithmetic average of the properties of the polymer constituting the polymer. When the constituent polymer is optically transparent, the resin composite is usually transparent.

The presence of two Tg's between TgC and TgL, or in agreement with these Tg's, generally indicates that the polymer constituting the resin composite is phase-separated. The mechanical properties of this resin composite are
It is known that it may be higher or lower than a (pseudo) compatible system, and may vary greatly depending on the shape of phase separation. Optically, it is usually opaque.

In the case of the resin composite of the present invention, it is possible to obtain characteristics exceeding the mechanical characteristics of the resin composite in a (pseudo) compatible state. Regarding transparency, the resin composite of the present invention can be formed into an optically transparent molded product while being phase-separated. In the case of a transparent molded product, the parallel light transmittance in the visible light region is preferably 70% or more, and 80% or more.
More preferably, it is the above.

The resin composite of the present invention can be formed into a molded article having an arbitrary shape. Examples of the shape that the molded product made of the resin composite of the present invention can take include a coating film, a film (including a sheet and a ribbon), a thin film, a fiber, a cast material, an impregnated material, and other complicated shapes. . However, due to the use of the active energy ray cross-linked polymer as the cross-linked polymer, it is necessary that the thickness be such that the active energy ray can reach, the thickness is preferably less than 5 mm, and the thickness is thin and constant. Is preferred. Therefore, although it depends on the use, it is preferably in the form of a film or a coating having a thickness of preferably 300 μm or less, more preferably 200 μm or less. When a particularly high transparency is required, a film or coating having a film thickness of 10 μm or less is preferable.

The active energy ray-crosslinkable polymer constituting the resin composite of the present invention is an active energy ray-crosslinkable polymerizable compound, ie, a compound which is cured by an active energy ray to become a crosslinked polymer, is cured by irradiation with an active energy ray. Is a crosslinked polymer.

The active energy ray-crosslinkable polymerizable compound used in the present invention is a urethane (meth) acrylate having 2 to 6 (meth) acryloyl groups in one molecule.
Urethane (meth) acrylate is a general term for poly (meth) acrylate having one or more urethane bonds as a linking group. Urethane (meth) acrylate is obtained, for example, by reacting a hydroxy compound having at least one (meth) acryloyloxy group with a polyfunctional isocyanate compound.

Examples of the hydroxy compound having at least one (meth) acryloyloxy group include, for example, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) ) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate,
Pentaerythritol tri (meth) acrylate, glycerol di (meth) acrylate, glycidyl (meth)
(Meth) acrylic acid adduct of acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate,
(Meth) acrylate compounds having various hydroxyl groups and ε
And ring-opening reaction products with caprolactone.

Examples of the polyfunctional isocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate,
m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
4,4′-diphenylmethane diisocyanate, 3,
Aromatic diisocyanates such as 3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexyl Aliphatic or alicyclic diisocyanates such as methane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; one or more burettes of isocyanate monomer, or a polyisocyanate having an isocyanurate ring obtained by trimerizing the diisocyanate compound A polyisocyanate obtained by a urethanization reaction of the above isocyanate compound and various polyols, and the like.

Examples of the polyol used for producing the polyisocyanate include (poly) alkylene glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, and (poly) tetramethylene glycol; Ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol,
Alkylene glycols such as diglycerin, ditrimethylolpropane, and dipentaerythritol, ethylene oxide-modified, propylene oxide-modified, butylene oxide-modified, tetrahydrofuran-modified, ε-caprolactone-modified, γ-butyrolactone-modified, δ-
Valerolactone modified product, methyl valerolactone modified product, etc .; copolymer of ethylene oxide and propylene oxide, copolymer of propylene glycol and tetrahydrofuran, copolymer of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene Hydrocarbon-based polyols such as glycol and hydrogenated polybutadiene glycol; aliphatic polyester polyols which are esterification products of aliphatic dicarboxylic acids such as adipic acid and dimer acid with polyols such as neopentyl glycol and methylpentanediol Aromatic polyester polyols which are esterification products of an aromatic dicarboxylic acid such as terephthalic acid and a polyol such as neopentyl glycol;
Polycarbonate polyols; Acrylic polyols; Polyhydric hydroxyl compounds such as polytetramethylene hexaglyceryl ether (modified tetrahydrofuran of hexaglycerin); Mono- and poly-substituted compounds having terminal hydroxyl groups of the above polyhydric hydroxyl-containing compounds; A polyvalent hydroxyl-containing compound obtained by esterification of a hydroxyl-containing compound with a dicarboxylic acid such as fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid; a polyvalent hydroxyl compound such as glycerin; Examples include, but are not limited to, polyhydric hydroxyl group-containing compounds such as monoglycerides obtained by transesterification with animal and plant fatty acid esters.

Among the urethane (meth) acrylates having 2 to 6 (meth) acryloyl groups in one molecule, preferred compounds include, for example, those represented by the general formula (1)

[0038]

Embedded image

(Wherein R ¹ is an alkylene group which may have a substituent, a metaphenylene group which may have a substituent or a compound represented by the formula (2)

[0040]

Embedded image

Wherein R ² is —CH ₂ CH
₂ OCOCX = CH ₂ , -CH (-CH ₂ OCOCX = CH ₂ ) ₂ , -C (-CH ₂ OCOCX = CH ₂ )
₃ or _{-CH (-CH 2 OC 6 H 5} ) (- CH 2 OCOCX = CH 2) represents, X
Represents a hydrogen atom or a methyl group. )).

In the above general formula, R ¹ has ¹ carbon atom.
To 18, preferably alkylene having 2 to 9 carbon atoms, and a poly (1
-Methylethane-1,2-diyl), poly (1-methylpropane-1,3-diyl), poly (2-methylpropane-1,3-diyl), poly (2,2-dimethylpropane-1,3-diyl) Diyl), poly (2,2-diethylpropane-1,3-diyl), poly (2-methyl-2-ethylpropane-1,3-diyl); 3-methylpentane-
1,5-diyl, 2-methyloctane-1,8-diyl, 2-hydroxymethyl-propane-1,3-diyl, 1-methyl-2,4-phenylene and the above formula (1)
The group represented by is particularly preferred.

The active energy ray-crosslinkable polymerizable compound is a compound of another type of active energy ray-crosslinkable polymerizable with these urethane (meth) acrylates and / or copolymerizable with them, such as another type of (meth) acrylate. And acrylate. In addition, in order to control the properties of the resin composite, the active energy ray crosslinked polymer,
It is also possible to use a copolymer of an active energy ray crosslinkable polymerizable compound and a monofunctional active energy ray polymerizable compound that does not give a crosslinked polymer by itself.

Examples of the monofunctional (meth) acrylic monomer that can be used as the monofunctional active energy ray polymerizable compound include, for example, methyl methacrylate, alkyl (meth) acrylate, isobornyl (meth) acrylate, and alkoxy polyethylene. Glycol (meth) acrylate, phenoxydialkyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol acrylate methacrylate, Butanediol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyl Roxyethyl-2-hydroxypropyl acrylate, ethylene oxide-modified phthalic acid acrylate, ω-alkoxycaprolactone monoacrylate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid, acrylic acid dimer, 2-acryloyloxypropyl hexahydro Examples thereof include hydrogen phthalate, fluorine-substituted alkyl (meth) acrylate, chlorine-substituted alkyl (meth) acrylate, and (meth) acrylate having a silano group.

Examples of the monofunctional maleimide monomer which can be used as a monofunctional active energy ray polymerizable compound include N-methylmaleimide, N-ethylmaleimide,
N-alkylmaleimides such as N-butylmaleimide, N-dodecylmaleimide; N-alicyclic maleimides such as N-cyclohexylmaleimide; N-benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide, N- Dialkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide, 2,3-
N- (substituted or unsubstituted phenyl) maleimide such as dichloro-N- (2,6-diethylphenyl) maleimide, 2,3-dichloro-N- (2-ethyl-6-methylphenyl) maleimide; N-benzyl- 2,3-dichloromaleimide, N- (4′-fluorophenyl) -2,3-
A maleimide having a halogen such as dichloromaleimide; a maleimide having a hydroxyl group such as hydroxyphenylmaleimide; a maleimide having a carboxy group such as N- (4-carboxy-3-hydroxyphenyl) maleimide; and an alkoxy group such as N-methoxyphenylmaleimide. Maleimide having an amino group such as N- [3- (diethylamino) propyl] maleimide; polycyclic aromatic maleimide such as N- (1-pyrenyl) maleimide; N- (dimethylamino-4-methyl-
3-coumarinyl) maleimide, N- (4-anilino-1)
And maleimides having a heterocyclic ring such as -naphthyl) maleimide.

Further, in order to control the properties of the resin composite, the active energy ray crosslinked polymer may be a copolymer containing a crosslinkable polymerizable oligomer (also called a prepolymer) as one component. It is possible. As the prepolymer, for example, a weight average molecular weight of 500 to 500
For example, (meth) acrylate of epoxy resin and (meth) of polyether resin
Acrylic esters, (meth) acrylic esters of polybutadiene resins, polyurethane resins having a (meth) acryloyl group at the molecular terminal, and the like are included.

The thermoplastic resin used in the present invention includes a polycarbonate polymer, a polyester polymer, a phenoxy resin, a vinyl acetal polymer, a vinyl chloride polymer, a vinyl acetate polymer, a styrene polymer, and a urethane. A thermoplastic resin selected from the group consisting of a system polymer, an uncrosslinked rubber, and a cellulose derivative, which is uniformly mixed with the active energy ray crosslinkable polymerizable compound used in the present invention. It is preferable that the temperature for uniformly dissolving is 200 ° C. or less. When such a thermoplastic resin is used in combination with the active energy ray-crosslinkable polymerizable compound used in the present invention, the thermoplastic resin is uniformly mixed with the active energy ray-crosslinkable polymerizable compound used in the present invention at a temperature of 200 ° C. or lower. It is easy to form a good co-continuous structure and easily obtain improved characteristics. Of course, the thermoplastic resin can be used alone, or two or more kinds can be used in combination.

The thermoplastic resin referred to in the present invention refers to a polymer that is not a crosslinked polymer, and includes a linear polymer and a branched polymer. Therefore, it also includes a polymer having a softening point higher than the decomposition temperature and showing no thermoplasticity. The thermoplastic resin used in the present invention may be amorphous or crystalline. In the case of a crystalline polymer, the melting point is preferably 200 ° C. or less,
More preferably, the temperature is 150 ° C. or lower. Those having a melting point higher than this tend to have poor compatibility with the active energy ray crosslinkable polymerizable compound at a temperature of 200 ° C. or lower.

Examples of the polycarbonate polymer usable in the present invention include bisphenol-A type and bisphenol-
Examples include F-type or bisphenol-Z type polycarbonates, copolymers thereof, and substituted products thereof.

Examples of the polyester polymer which can be used in the present invention include a condensed polymer of a polyvalent carboxylic acid and a polyhydric alcohol, a copolymer thereof, and a substituted product thereof.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexamethylenediol, octanediol, neopentyl glycol, cyclohexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, Examples thereof include polypropylene glycol and polytetramethylene glycol, and two or more of these can be used. Among these, ethylene glycol, propylene glycol, butylene glycol,
Hexamethylenediol and neopentyl glycol are particularly preferred.

Examples of the polycarboxylic acid include aromatic carboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; carbon atoms such as succinic acid, adipic acid, azelaic acid, sebacic acid, brassic acid and cyclohexanedicarboxylic acid. An aliphatic dicarboxylic acid of the formulas 4 to 14;
Examples thereof include dimer acid, trimellitic acid, pyromellitic acid, trimellitic anhydride, and pyromellitic anhydride. These polyhydric carboxylic acids may be used in combination of two or more. Among them, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid and cyclohexanedicarboxylic acid are particularly preferred.

As the polyester polymer that can be used in the present invention, lactone polyesters such as polyε-caprolactone and polybutyrolactone can also be used.

The phenoxy resin that can be used in the present invention is a reaction product of epichlorohydrin and a bisphenol compound and has no epoxy group at the terminal. Among such phenoxy resins, a phenoxy resin obtained from epichlorohydrin and bisphenol A is particularly preferred.

Examples of the vinyl acetal polymer that can be used in the present invention include polyvinyl formal, polyvinyl acetal, copolymers thereof, and substituted products thereof. Among these vinyl acetal polymers, polyvinyl formal and polyvinyl acetal are particularly preferred.

Examples of the vinyl chloride polymer usable in the present invention include vinyl chloride, chlorinated polyethylene and chlorinated polypropylene. Chlorinated polyethylene and chlorinated polypropylene have a chlorine content of 50%
The above-mentioned highly chlorinated polymers are preferred.

Examples of the vinyl acetate-based polymer that can be used in the present invention include vinyl acetate, copolymers thereof, and substituted products thereof. Among these vinyl acetate polymers,
Polyvinyl acetate, ethylene-vinyl acetate copolymer (EV
A) is particularly preferred.

The styrenic polymers usable in the present invention include polystyrene, copolymers thereof, and substituted products thereof. Among these styrene polymers, poly-α-methylstyrene, styrene-methyl methacrylate copolymer (MS), styrene-acrylonitrile copolymer (AS), styrene-maleic anhydride copolymer (SM)
AA) and styrene-maleic acid copolymer are particularly preferred.

The urethane polymers usable in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisoanate, xylylene diisocyanate, and the like.
Polymers of isocyanates such as dicyclohexylmethane diisocyanate and polyester polyols such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, and polycaprolactone, and polyether polyols such as polyoxypropylene diol, polytetramethylene glycol ether, and polyoxyethylene diol Thermoplastic polyurethane, and the like. Among these urethane polymers, as the isocyanate, tolylene diisocyanate or diphenylmethane diisocyanate was used, and as the polyol, 1,4-butanediol, 1,6-hexanediol, a polyester polyol of neopentyl glycol and adipic acid was used. Are preferably used.

The uncrosslinked rubber that can be used in the present invention includes:
Butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SB
R) or the like; isoprene-based rubber such as chloroprene rubber or isoprene rubber; and acrylic rubber (A
R). Among these uncrosslinked rubbers, NB
R, SBR and AR are particularly preferred.

The cellulose derivatives usable in the present invention include organic acid celluloses such as cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate; methylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, ethylcellulose, ethylhydroxyethylcellulose, and the like. Cellulose ethers such as hydroxyethylcellulose, carboxymethylhydroxyethylcellulose, sodium carboxymethylcellulose, and hydroxypropylcellulose; nitrocellulose,
Examples include inorganic cellulose such as cellulose sulfate and cellulose phosphate. Among these cellulose derivatives,
Ethyl cellulose, cellulose acetate and nitrocellulose are particularly preferred.

Incidentally, among the thermoplastic resins, polyether sulfone and polysulfone have an excessively low compatibility with the active energy ray crosslinkable polymerizable compound used in the present invention.
It is not preferable because it is considerably difficult to obtain a resin composite having a bicontinuous structure.

When these thermoplastic resins are used in combination with the active energy ray-crosslinkable polymerizable compound used in the present invention, a good co-continuous structure can be easily formed and the properties can be improved. ,
(1) In the general formula (1), R ¹ has 2 carbon atoms.
And R ² is -C (CH ₂ OCOCX = CH ₂ ) ₃
(Wherein X is hydrogen or a methyl group) from a hexa (meth) acrylate compound, a vinyl acetal polymer, a vinyl acetate polymer, a styrene polymer, a urethane polymer, an uncrosslinked rubber and a cellulose derivative. A combination with one or more thermoplastic resins selected from the group consisting of:

(2) In the general formula (1), R ¹ is alkylene having 2 to 9 carbon atoms, and R ² is —CH (C
A tetra (meth) acrylate compound which is H ₂ OCOCX = CH ₂ ) ₂ (where X is hydrogen or a methyl group), a polyester polymer, a phenoxy resin, a vinyl acetal polymer,
A combination with one or more thermoplastic resins selected from the group consisting of vinyl chloride-based polymers, vinyl acetate-based polymers, styrene-based polymers, urethane-based polymers, uncrosslinked rubbers and cellulose derivatives,

(3) In the general formula (1), R ¹ is alkylene having 2 to 9 carbon atoms, and R ² is —CH (C
A di (meth) acrylate compound which is H ₂ OC ₅ H ₆ ) (CH ₂ OCOCX = CH ₂ ) (where X is hydrogen or a methyl group), a polyester polymer, a phenoxy resin, a vinyl acetal polymer, A combination with one or more thermoplastic resins selected from the group consisting of vinyl chloride-based polymers, vinyl acetate-based polymers, styrene-based polymers, urethane-based polymers and uncrosslinked rubbers,

(4) In the general formula (1), R ¹ is 1-methyl-2,4-phenylene and R ² is -C (CH
₂ OCOCX = CH ₂ ) ₃ (where X is hydrogen or a methyl group), a polyester (meth) acrylate polymer, a vinyl acetal polymer, a vinyl chloride polymer, and a vinyl acetate polymer A combination with one or more thermoplastic resins selected from the group consisting of styrene-based polymers, urethane-based polymers, uncrosslinked rubbers and cellulose derivatives,

(5) In the general formula (1), R ¹ is 1-methyl-2,4-phenylene, and R ² is —CH (C
A di (meth) acrylate compound which is H ₂ OC ₅ H ₆ ) (CH ₂ OCOCX = CH ₂ ) (where X is hydrogen or a methyl group), a polycarbonate-based polymer, a polyester-based polymer, a phenoxy resin, and vinyl Particularly preferred is a combination of at least one resin selected from the group consisting of an acetal-based polymer, a vinyl chloride-based polymer, a vinyl acetate-based polymer, a styrene-based polymer, a urethane-based polymer, and an uncrosslinked rubber.

The mixing ratio of the active energy ray-crosslinkable polymerizable compound and the thermoplastic resin varies depending on the type of the resin used, but usually, the mixing weight ratio of (active energy ray-crosslinked polymer: thermoplastic resin) is (98%). : 2)-(10:90)
Is preferable, and the range of (95: 5) to (20:80) is particularly preferable.

In the resin composite of the present invention, it is possible to obtain a composite having excellent mechanical properties to which toughness, which is a characteristic of a thermoplastic resin, is provided. , The characteristics of each resin are given. For example, when an aromatic polyester-based polymer or a vinyl chloride-based polymer is used as the thermoplastic resin, a high elastic modulus and surface hardness can be effectively imparted to the resin composite, and the thermoplastic resin When a polycarbonate, urethane-based polymer, vinyl acetate-based polymer or uncrosslinked rubber is used, it is possible to effectively impart elongation at break and impact resistance to the resin composite, When a phenoxy resin or a cellulose derivative is used as the resin, high surface affinity can be effectively imparted to the resin composite.

The resin composite of the present invention contains other components,
For example, lubricants such as fluorine compounds and silicones; coloring agents such as dyes, pigments and fluorescent dyes and ultraviolet absorbers; antioxidants; antifungal agents; antibacterial agents; inorganic and organic powders; It can be contained in the form of a polymerization.
It is also possible to use a composite such as a fiber reinforced plastic or a laminate sheet.

The resin composite of the present invention can be produced, for example, by the following production method of the present invention.

That is, in the production method of the present invention, an active energy beam crosslinkable polymerizable compound and a thermoplastic resin are mixed and mixed into a homogeneous mixture (hereinafter, this homogeneous mixture is simply referred to as “homogeneous mixture”). May be prepared). After shaping the homogeneous mixed solution, an active energy ray is irradiated to harden the shaped product of the uniform mixed solution, induce phase separation, and fix the bicontinuous structure.

The active energy ray-crosslinkable polymerizable compound used in the production method of the present invention is a urethane (meth) acrylate having 2 to 6 (meth) acryloyl groups in one molecule. It is possible to form a uniform mixture with the thermoplastic resin used. The active energy ray crosslinkable polymerizable compound used in the production method of the present invention is the same as described for the active energy ray crosslinkable polymerizable compound in the resin composite of the present invention.

For the purpose of increasing the compatibility between the active energy ray-crosslinkable polymerizable compound and the thermoplastic resin and controlling the reactivity of the homogeneous mixture, a monofunctional solution which does not give a crosslinked polymer alone to the homogeneous mixture is used. Can be used in combination. The monofunctional active energy ray polymerizable compound is arbitrary as long as it is capable of copolymerizing with the active energy ray crosslinkable polymerizable compound by irradiation with active energy rays to give a crosslinked polymer. The monofunctional active energy ray polymerizable compound is the same as described for the monofunctional active energy ray polymerizable compound composition in the resin composite of the present invention.

The thermoplastic resin used in the production method of the present invention includes a polycarbonate polymer, a polyester polymer, a phenoxy resin, a vinyl acetal polymer, a vinyl chloride polymer, a vinyl acetate polymer, and a styrene polymer. A thermoplastic resin selected from the group consisting of a coalescable, urethane-based polymer, uncrosslinked rubber, and a cellulose derivative, and preferably forms a homogeneous mixture with the active energy ray-crosslinked polymerizable compound to be used at a temperature of 200 ° C. or lower. It is possible to do. The thermoplastic resin used in the production method of the present invention can be selected from those exemplified as the thermoplastic resins that can be used in the resin composite of the present invention. Of course, the thermoplastic resins can be used alone or in combination of two or more.

The homogeneous liquid mixture used in the production method of the present invention is a liquid mixture in which an active energy ray crosslinkable polymerizable compound and a thermoplastic resin are uniformly mixed. However, for example, the presence of a very small amount of insoluble portion due to the molecular weight distribution of the chain polymer is acceptable.

The viscosity of the homogeneous mixture used in the production method of the present invention is considered to be an important factor affecting the production conditions for obtaining the phase separation structure of the present invention. The optimum viscosity range greatly differs depending on the combination with the plastic resin, the composition ratio thereof, the active energy ray intensity, the reaction temperature and the like. For this reason, the viscosity of the homogeneous mixture cannot be specified unconditionally, but the viscosity at the active energy ray irradiation temperature is 1 to 1,000,000 cps.
Is preferably in the range of ^{(10 -3 ~10 2 Pa · s} ), 5~1
The range of 0000 cps (5 × 10 ^{−3 to} 10 Pa · s) is more preferable.

The homogeneous mixed solution used in the production method of the present invention contains, in addition to the active energy ray-crosslinkable polymerizable compound and the thermoplastic resin, for example, a photopolymerization initiator; a coloring agent such as a dye, a pigment, a fluorescent dye; UV absorbers; antioxidants; inorganic or organic powders; reinforcing fibers and the like can also be included.

When light such as ultraviolet light, visible light, or infrared light is used as the active energy ray used in the production method of the present invention, a photopolymerization initiator is added to the homogeneous mixture for the purpose of increasing the polymerization rate. Is preferred.

The photopolymerization initiator, which can be added to the homogeneous mixture as required, is active with respect to the light beam used in the present invention, and is capable of crosslinking and polymerizing the active energy ray crosslinkable polymerizable compound. There is no particular limitation as long as it is a radical polymerization initiator, for example, a radical polymerization initiator, an anionic polymerization initiator, or a cationic polymerization initiator.

As such a photopolymerization initiator, for example, p-tert-butyltrichloroacetophenone, 2,2
2'-diethoxyacetophenone, 2-hydroxy-2
Acetophenones such as -methyl-1-phenylpropan-1-one; benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone,
Ketones such as 2-methylthioxanthone, 2-ethylthioxanthone and 2-isopropylthioxanthone;
Benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone; and maleimides.

The photopolymerization initiator can be used in the state of being dissolved or dispersed in a homogeneous mixture, but is preferably one that dissolves in the homogeneous mixture. When using a photopolymerization initiator, the photopolymerization initiator concentration in the homogeneous mixture is 0.0
The range of 1 to 20% by weight is preferable, and 0.5 to 10% by weight.
Is particularly preferred. However, this is not the case when the active energy ray crosslinkable polymerizable compound also functions as a photopolymerization initiator or when the active energy ray crosslinkable polymerizable compound is a photopolymerization initiator copolymerized with the active energy ray crosslinkable polymerizable compound.

The homogeneous mixture is preferably at 0 to 200 ° C.
More preferably, it is prepared in a temperature range of 10 to 180 ° C. The method of preparing the homogeneous mixed solution can be a method of dissolving the thermoplastic resin in the crosslinkable polymerizable compound by a method such as heating, but after dissolving the thermoplastic resin and the crosslinkable polymerizable compound in a solvent in which both are soluble. It is also preferable to remove the solvent and obtain a homogeneous mixed solution. By using a solvent, the time required for mixing the thermoplastic resin and the crosslinkable polymerizable compound can be significantly reduced, and a homogeneous mixed solution having a high viscosity can be obtained.

When a solvent is used in preparing the homogeneous mixture, any solvent can be used as long as it can be removed by some method such as evaporation or extraction, but a volatile solvent may be used. preferable. Although a high boiling point solvent such as N-methylpyrrolidone or dimethyl sulfoxide can be used, the boiling point of the solvent is preferably 150 ° C. or lower, more preferably 120 ° C. or lower.

Examples of such a solvent include chlorine solvents such as methylene chloride, chloroform, trichloroethane and tetrachloroethane; ketone solvents such as acetone and 2-butanone; ester solvents such as ethyl acetate and butyl acetate. Ether solvents such as diethyl ether, dibutyl ether and tetrahydrofuran; hydrocarbon solvents such as toluene and cyclohexane; amide solvents such as dimethylformamide and dimethylacetamide; acids such as formic acid; phenols such as chlorophenol; Solvents having two or more kinds of functional groups in one molecule such as butyl cellosolve; liquefied gases such as liquefied carbon dioxide and liquefied ammonia; and supercritical fluids such as supercritical carbon dioxide.

The method of removing the solvent is optional, but removal by volatilization is preferred. The volatilization method is also arbitrary, and may be, for example, air drying, hot air drying, infrared drying, vacuum drying, or the like. The solvent may remain as long as it does not significantly affect the phase separation structure formed by the subsequent shaping and active energy ray irradiation. A slight change in viscosity or change in compatibility can be corrected under the active energy ray irradiation conditions.

The homogeneous mixture is formed into an arbitrary shape such as a coating film, a film (including a sheet and a ribbon), a fiber, a cast, and an impregnated material. However, it is necessary that the shape be curable by active energy rays. For example, it is necessary that the active energy ray has a thickness that can be reached, and when the shaped object is covered with a coating, the coating needs to transmit the active energy ray to be used. The shaping method is also arbitrary, for example, coating, casting,
It can be dipping, spraying, casting, impregnating, extruding, etc.
When the preparation of the homogeneous mixture is a method using a solvent, the shaping may be performed before, after, or after partial removal of the solvent. When the viscosity of the homogeneous mixed solution is high, or when the shaped product has a small thickness such as a coating film or a film, it is also preferable to remove the solvent after the shaping.

Next, the shaped product of the homogeneous mixture is irradiated with an active energy ray at a predetermined temperature. The irradiation temperature of the active energy ray needs to be a temperature at which the homogeneous mixture maintains a compatible state, that is, a temperature at which phase separation does not occur before irradiation. At this time, the homogeneous mixture may be in a supercooled state.
The determination of the compatibility state of the mixed liquid is performed by visually confirming the transparency,
Alternatively, it can be performed by optical microscope observation.

When the homogeneous mixture is irradiated with active energy rays, microphase separation proceeds with the progress of polymerization of the crosslinkable polymerizable compound. However, since the active energy ray crosslinkable polymerizable compound forms a crosslinked structure by polymerization, The structure is fixed at any stage during the separation process. The resin composite of the present invention can be obtained by controlling the compatibility of the components of the homogeneous mixture, the viscosity of the homogeneous mixture, the irradiation temperature of the active energy ray, and the intensity of the active energy ray. The conditions for forming the resin composite of the present invention differ depending on the combination of the active energy ray crosslinkable polymerizable compound and the thermoplastic resin, and cannot be unconditionally specified. However, if the conditions of good compatibility, high viscosity, low irradiation temperature, and high active energy ray intensity are excessive, the structure is solidified before the phase separation proceeds, and a bicontinuous structure is not observed. A (pseudo) compatible structure exhibiting Tg is obtained. Conversely, if the conditions of poor compatibility, low viscosity, high temperature, and low strength are excessive, the phase separation proceeds excessively to form a sea-island type phase separation structure, resulting in a decrease in mechanical properties. Normal,
Since the compatibility and viscosity are determined by the system, when the system is fixed, the parameters that are mainly controlled are the irradiation temperature and the active energy ray intensity, and their time programs. By appropriately adjusting these, it is possible to optimize the target structure and characteristics. In order to shorten the time to complete curing without changing the structure of the resin composite,
It is also preferred to raise the temperature in the latter half of the curing step.

The active energy ray used in the production method of the present invention is not particularly limited as long as it can cure a homogeneous mixture, and includes, for example, light rays such as ultraviolet rays, visible rays and infrared rays; X-rays and gamma rays. And ion beams such as electron beams, beta rays, neutron beams, and heavy ion beams. Among these, a light beam is preferable from the viewpoint of handleability and an apparatus price, and an ultraviolet light is particularly preferable. In the case of full surface irradiation, the ultraviolet intensity is 0.1 to 1000 mW / cm ²
It is preferred that The ultraviolet light is preferably a laser beam. The irradiation may be a patterning irradiation as needed.

For the purpose of accelerating the curing speed and performing the curing completely, it is preferable to carry out the irradiation with the active energy ray in a low oxygen concentration atmosphere. The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere.

The cured resin composite of the present invention can be subjected to a heat treatment if necessary. The heat treatment can further improve the properties and increase the thermal stability.

[0093]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited to the scope of the following examples.

In the following examples, a 160 W metal halide lamp (manufactured by Eye Graphics) was used as an ultraviolet ray source. UV irradiation intensity is about 70mW / cm
^{Was 2} . The ultraviolet irradiation time was 90 seconds.

Next, a method of measuring a glass transition temperature, a method of measuring a tensile fracture, a method of measuring a light transmittance, and a method of observing a phase separation structure in the following examples will be described.

(Measurement of glass transition temperature) The glass transition temperature (Tg) is obtained by measuring the temperature change of the complex elastic modulus at 1 Hz by a dynamic viscoelasticity measurement method and obtaining a peak of tan δ (loss elastic modulus / storage elastic modulus). Evaluated by temperature. For dynamic viscoelasticity measurement, "RSA-II" manufactured by Rheometrics Co., Ltd. was used. The heating rate was 2 ° C. per minute. When the sample was a coating film, a film-like material peeled from the substrate was measured.

(Tensile Breaking Test) In the tensile breaking test, a tensile tester (Autograph AGS-H) manufactured by Shimadzu Corporation was used. When the sample was a coating film, a film-like material peeled from the substrate was used. Width 3mm, thickness about 0.1mm
The test was performed at a sample length of 10 mm and a tensile speed of 5 mm per minute.

(Measurement of Light Transmittance) Using a turbidity meter “NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd., the parallel light transmittance of the coating film or film was measured. Film thickness is 1
00 ± 20 μm.

(Observation of Phase Separation Structure) The observation of the phase separation structure was carried out using a transmission electron microscope (“J.
EM-200 "; hereinafter, abbreviated as" TEM ". ) Was used. Ultra-thin section of film section and coating section (about 50n
m) was prepared and used as a sample. Depending on the resin used,
To increase the contrast, staining was performed with ruthenium tetroxide, osmium tetroxide, iodine, and the like.

Example 1 As an active energy ray crosslinkable polymerizable compound, "urethane acrylate AT-60" was used.
0 ”(Kyoeisha Chemical Co., Ltd.

[0101]

Embedded image

Diacrylate which is a reaction product of 2-hydroxy-3-phenoxypropyl acrylate and tolylene diisocyanate represented by the following formula;
0 ”. ) 5 g, 0.1 g of "Irgacure 184" (1-hydroxycyclohexyl phenyl ketone manufactured by Ciba Geigy) as a photopolymerization initiator and "Iupilon Z-200" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a thermoplastic resin. Bisphenol-Z type polycarbonate; hereinafter, abbreviated as "PCz") was dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (1).

After the thus obtained homogeneous mixed solution (1) was applied on a glass plate, the solvent was volatilized to obtain an uncured coating film of the homogeneous mixed solution. Next, a cover of a glass plate was closely attached to this coating film, and the uncured shaped material was sandwiched between two glass plates.

When the temperature of the shaped object was raised on a stage whose temperature was adjusted together with the glass plate, the shaped object was heated from room temperature (25 ° C.) to 1 ° C.
It was colorless and transparent at 20 ° C. The cross-linked polymerizable compound was polymerized by irradiating ultraviolet rays while maintaining the excipient at 120 ° C., and the excipient was cured.

A film (thickness = about 100 μm) obtained by peeling the obtained cured product from the glass plate was colorless and transparent at room temperature, and the light transmittance of the coating film was 90%. In this film, two Tg were observed at about 78 ° C. and about 150 ° C. As a result of observing the cross section of the film using a TEM, a network-like phase-separated structure having a diameter of 40 to 60 nm could be observed. When the film was immersed in methylene chloride for 1 hour, no change was observed in the shape of the film except that the film was slightly swollen. Further, methylene chloride in which the film was immersed for 1 hour was applied to a glass plate, and the dried product was observed with a scanning electron microscope (SEM: manufactured by Hitachi, Ltd., Model S-800). Did not.

The strength, elongation at break, and
Table 1 shows the measurement results of the elastic modulus and the breaking energy. As a result, the film-shaped cured product made of the resin composite obtained in Example 1 has higher strength, elastic modulus, elongation at break, and breaking energy than the cured products of Reference Example 1 and Comparative Example 1 described later. It can be seen that it has improved.

[Comparative Example 1] A crosslinked polymerizable compound obtained by irradiating an uncured excipient prepared in Example 1 with ultraviolet rays at room temperature (25 ° C) at a state sandwiched between two glass plates was used. Was polymerized to cure the excipient.

The film (film thickness = about 100 μm) obtained by peeling the cured product from the glass plate was colorless and transparent at room temperature. The Tg of this film was measured to be 80
One tan δ peak could be observed around ℃.
The cross section of the film was observed using a TEM, but it was homogeneous and no phase-separated structure could be observed. It is presumed to be in a (pseudo) compatible state. Table 1 shows the measurement results of the strength, breaking elongation, elastic modulus, and breaking energy of the cured film product obtained in Comparative Example 1.

[Reference Example 1] In Example 1, no thermoplastic resin was used, no solvent was used, no glass plate cover was attached, and the irradiation temperature was 25 ° C. Except for the above, a film-like cured product of “AT600” (film thickness = about 110 μm) was obtained in the same manner as in Example 1. Table 1 shows the measurement results of the strength, breaking elongation, elastic modulus, and breaking energy of the film-shaped cured product obtained in Reference Example 1.

[Example 2] In Example 1, "AT6
00, Irgacure 184 and PCz were changed to 8 g, 0.16 g and 2 g, respectively, and the ultraviolet irradiation temperature was set to 80 ° C., and a film was produced in the same manner as in Example 1. The uncured excipient at the UV irradiation temperature was transparent, but the cured film was
It was cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.4 to 0.6 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1.

The strength of the cured film obtained in Example 2,
Table 1 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the cured film obtained from the resin composite obtained in Example 2 had the same elastic modulus as the single cured product of “AT600” (Reference Example 1), but the strength,
It can be seen that the breaking elongation and the breaking energy are greatly improved.

[Embodiment 3] In the embodiment 1, "AT6
00, Irgacure 184, and PCz were changed to 3 g, 0.06 g, and 7 g, respectively, and the ultraviolet irradiation temperature was set to 170 ° C., and a film was produced in the same manner as in Example 1. The uncured excipient at the ultraviolet irradiation temperature was transparent, but the cured film was colorless and transparent, and the light transmittance was 90%.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 30 to 50 nm could be observed. The results of the solvent extraction test were the same as in Example 1.

The strength of the cured film obtained in Example 3
Table 1 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the cured film obtained from the resin composite obtained in Example 3 had significantly improved strength, elastic modulus, elongation at break and elongation at break as compared with the cured product of AT600 alone (Reference Example 1). You can see that there is.

[0116]

[Table 1]

Example 4 8 g of "AT600" as an active energy ray crosslinkable polymerizable compound, 0.16 g of "Irgacure 184" as a photopolymerization initiator and polyvinyl chloride (Wako Pure Chemical Industries, Ltd.) as a thermoplastic resin Made by company)
2 g was dissolved in 50 g of tetrahydrofuran (THF) to obtain a homogeneous mixed solution (4).

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (4) was used in place of the homogeneous mixed solution (1), and that the UV irradiation temperature was 80 ° C. Produced. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and cloudy, and the light transmittance of the film was 78%.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.2 to 0.5 μm could be observed. Further, the result of the solvent extraction test performed in the same manner as in Example 1 except that THF was used instead of methylene chloride in Example 1, the results were the same as in Example 1.

The strength of the cured film obtained in Example 4
Table 2 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, it can be seen that the strength, the elastic modulus, the elongation at break, and the energy at break are improved as compared with the single cured product of “AT600” (Reference Example 1).

Example 5 8 g of "AT600" as an active energy ray crosslinkable polymerizable compound, 0.16 g of "Irgacure 184" as a photopolymerization initiator, and polyvinyl formal (available from Scientific Polymer Co., Ltd.) as a thermoplastic resin 2 g) was dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (5).

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (5) was used in place of the homogeneous mixed solution (1), and that the ultraviolet irradiation temperature was 80 ° C. Produced. The uncured excipient was colorless and transparent at room temperature or higher, but the cured film was thin and cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.2 to 0.6 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1.

The strength of the cured film obtained in Example 5
Table 2 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the cured film made of the resin composite obtained in Example 5 had almost the same elastic modulus as the cured product of “AT600” alone (Reference Example 1), but showed strength and elongation at break. It can be seen that the breaking energy has been greatly improved.

Example 6 In Example 5, "Pandex-T5205" was used in place of polyvinyl formal.
A homogeneous mixed solution (6) was obtained in the same manner as in Example 5, except that a thermoplastic polyurethane manufactured by Dainippon Ink and Chemicals, Inc .; hereinafter, abbreviated as “T5205” was used.

A film was produced in the same manner as in Example 1 except that the homogeneous mixed solution (6) was used in place of the homogeneous mixed solution (1), and the irradiation temperature of ultraviolet rays was 100 ° C. . The uncured excipient was colorless and transparent at room temperature or higher. Further, the cured film was thin and cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.2 to 0.4 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1.

The strength of the cured film obtained in Example 6
Table 2 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the cured film made of the resin composite obtained in Example 6 has almost the same strength and slightly lower elastic modulus than the cured product of “AT600” alone (Reference Example 1). It can be seen that the elongation at break significantly improved and the breaking energy was greatly improved.

[Comparative Example 2] The uncured shaped product prepared in Example 6 sandwiched between two glass plates was irradiated with ultraviolet rays at room temperature to polymerize the crosslinkable polymerizable compound. And the excipient was cured.

The obtained film was colorless and transparent. TEM observation of this film revealed that it was homogeneous and no phase-separated structure was observed.

The strength of the cured film obtained in Comparative Example 2
Table 2 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the cured film in Comparative Example 2 was significantly improved in elongation at break and breaking energy as compared with the cured product of AT600 alone (Reference Example 1). Compared with the cured film, the strength and elastic modulus were significantly reduced.

Example 7 In Example 5, polyvinyl acetate (Mw = about 26) was used instead of polyvinyl formal.
10,000; manufactured by Scientific Polymer Co., Ltd.), and a homogeneous mixed solution (7) was prepared in the same manner as in Example 5.
I got

A film was prepared in the same manner as in Example 1, except that the homogeneous mixed solution (7) was used in place of the homogeneous mixed solution (1), and that the UV irradiation temperature was 80 ° C. Produced. The uncured excipient was colorless and transparent at room temperature or higher, but the cured film was thin and cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.3 to 0.6 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1.

The strength of the cured film obtained in Example 7
Table 2 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the cured film made of the resin composite obtained in Example 7 had almost the same strength and elastic modulus as the cured product of “AT600” alone (Reference Example 1). It can be seen that the breaking energy has been greatly improved.

Example 8 Example 2 was repeated except that "Byron 500" (an aromatic polyester manufactured by Toyobo Co., Ltd.) was used instead of polyvinyl formal.
In the same manner as in Example 2, a homogeneous mixed solution (8) was obtained.

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (8) was used in place of the homogeneous mixed solution (1), and that the ultraviolet irradiation temperature was 80 ° C. Produced. The uncured excipient was colorless and transparent at room temperature or higher, but the cured film was thin and cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.3 to 0.8 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1.

The strength of the cured film obtained in Example 8
Table 2 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the cured film obtained from the resin composite obtained in Example 8 had almost the same strength and elastic modulus as the cured single product of “AT600” (Reference Example 1). It can be seen that the breaking energy has been greatly improved.

Example 9 8.5 g of AT600 as an active energy ray crosslinkable polymerizable compound, 0.17 g of "Irgacure 184" as a photopolymerization initiator, and "Nippol AR71" (Nippon Zeon Co., Ltd.) as a thermoplastic resin 1.5 g was dissolved in 70 g of methylene chloride to obtain a homogeneous mixed solution (9).

A film was prepared in the same manner as in Example 1, except that the homogeneous mixed solution (9) was used in place of the homogeneous mixed solution (1), and that the UV irradiation temperature was 80 ° C. Produced. The uncured excipient was colorless and transparent at room temperature or higher. Further, the cured film was thin and cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.5 to 0.8 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1.

The strength of the cured film obtained in Example 9
Table 2 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the cured film obtained from the resin composite obtained in Example 9 has almost the same strength and slightly lower elastic modulus than the cured product of AT600 alone (Reference Example 1). It can be seen that the breaking elongation and the breaking energy were greatly improved.

[0144]

[Table 2]

Example 10 As an active energy ray crosslinkable polymerizable compound, "urethane acrylate AH60
0 ”(Kyoeisha Chemical Co., Ltd. formula

[0146]

Embedded image

A diacrylate which is a reaction product of 2-hydroxy-3-phenoxypropyl acrylate and hexamethylene diisocyanate represented by the following formula:
00 ”. 8), 0.16 g of “Irgacure 184” as a photopolymerization initiator and 2 g of polyvinyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) as a thermoplastic resin were dissolved in 50 g of tetrahydrofuran (THF) to obtain a homogeneous mixed solution (10%). ) Got.

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (10) was used in place of the homogeneous mixed solution (1), and that the UV irradiation temperature was 80 ° C. Produced. Uncured excipients are at room temperature to 80 ° C
The film after curing was thin and cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.2 to 0.5 μm could be observed. Further, the result of the solvent extraction test performed in the same manner as in Example 1 except that THF was used instead of methylene chloride in Example 1, the results were the same as in Example 1.

Table 3 shows the measurement results of the strength, elongation at break, elastic modulus and energy at break of the cured film obtained in Example 10. As a result, it can be seen that the strength and the modulus of elasticity are almost the same as those of a single cured product of “AH600” described later (Reference Example 2), but the breaking elongation and the breaking energy are significantly improved.

[Comparative Example 3] The uncured excipient prepared in Example 10 was sandwiched between two glass plates and irradiated with ultraviolet rays at room temperature to polymerize the crosslinkable polymerizable compound. ,
The excipient was cured.

The obtained film was colorless and transparent. TEM observation of this film revealed that it was homogeneous and no phase-separated structure was observed.

The strength of the cured film obtained in Comparative Example 3
Table 3 summarizes the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the film-form cured product of Comparative Example 3 is significantly improved in elongation at break and energy at break as compared with a single cured product of “AH600” described later (Reference Example 2). Compared with the obtained cured film, the strength and elastic modulus were significantly reduced.

[Reference Example 2] In Example 10, no thermoplastic resin was used, no solvent was used, no glass plate cover was attached, and the irradiation temperature was 25 ° C. AH600 alone cured film (film thickness = about 110 μm) was obtained in the same manner as in Example 10 except for the above. Table 3 shows the measurement results of the strength, elongation at break, elastic modulus, and energy at break of the cured film obtained in Reference Example 2.

Example 11 The procedure of Example 10 was repeated, except that “PKHH” (phenoxy resin manufactured by Union Carbide Co., Ltd.) was used instead of polyvinyl chloride. Solution (11) was obtained.

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (11) was used in place of the homogeneous mixed solution (1), and that the UV irradiation temperature was 80 ° C. Produced. The uncured excipient was colorless and transparent at room temperature or higher, but the cured film was cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.3 to 0.6 μm could be observed. Further, the result of the solvent extraction test performed in the same manner as in Example 1 except that THF was used instead of methylene chloride in Example 1, the results were the same as in Example 1.

Table 3 shows the measurement results of the strength, elongation at break, elastic modulus, and energy at break of the cured film obtained in Example 11. As a result, the cured film obtained from the resin composite obtained in Example 11 had a slightly lower elastic modulus than the cured product of “AH600” alone (Reference Example 2), but the strength and fracture were high. It can be seen that elongation and breaking energy are greatly improved.

[0159]

[Table 3]

Example 12 As an active energy beam crosslinkable polymerizable compound, "urethane acrylate UA-10" was used.
1H ”(Kyoeisha Chemical Co., Ltd. formula

[0161]

Embedded image

Tetramethacrylate which is a reaction product of glycerol dimethacrylate and hexamethylene diisocyanate represented by the following formula; hereinafter abbreviated as "UA101H". ) 7 g, "Irgacure 1" as a photopolymerization initiator
84 "as a thermoplastic resin and" PKH
3 g of "H" was dissolved in 50 g of tetrahydrofuran (THF) to obtain a homogeneous mixed solution (12).

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (12) was used in place of the homogeneous mixed solution (1), and that the UV irradiation temperature was 80 ° C. Produced. Uncured excipients are at room temperature to 80 ° C
, And the film after curing was also transparent.
The light transmittance of the cured film was 89%.

When the film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.08 to 0.2 μm could be observed. Example 1
In the above, the result of the solvent extraction test carried out in the same manner as in Example 1 was the same as in Example 1, except that THF was used instead of methylene chloride.

Table 4 shows the measurement results of the strength, elongation at break, elastic modulus, and energy at break of the cured film obtained in Example 12. As a result, it can be seen that the characteristics are remarkably improved as compared with a single cured product of “UA101H” described later (Reference Example 3).

[Comparative Example 4] The uncured shaped material prepared in Example 12 sandwiched between two glass plates was irradiated with ultraviolet rays at room temperature to polymerize the crosslinkable polymerizable compound. ,
The excipient was cured.

The resulting film was colorless and transparent. TEM observation of this film revealed that it was homogeneous and no phase-separated structure was observed.

The strength of the cured film obtained in Comparative Example 4
Table 4 summarizes the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, the cured film in Comparative Example 4 had better characteristics than the UA101H alone cured product described later (Reference Example 3), but was inferior in all evaluation items compared to Example 12.

[Reference Example 3] In Example 12, no thermoplastic resin was used, no solvent was used, no glass plate cover was attached, and the irradiation temperature was 25 ° C. UA101H alone cured film (thickness =
About 110 μm). The cured film obtained in Reference Example 3 was very brittle and could not be subjected to a tensile fracture test.

Example 13 8 g of "UA101H" as an active energy ray crosslinkable polymerizable compound, 0.16 g of "Irgacure 184" as a photopolymerization initiator, 2 g of "Vylon 500" as a thermoplastic resin, and 50 g of methylene chloride To obtain a homogeneous mixed solution (13).

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (13) was used in place of the homogeneous mixed solution (1), and that the UV irradiation temperature was 80 ° C. Produced. The uncured excipient was cloudy at room temperature, but was colorless and transparent at 50 ° C. or higher. The cured film was cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.4 to 0.7 μm could be observed. The results of the solvent extraction test were the same as in Example 1.

Table 4 shows the measurement results of the strength, elongation at break, elastic modulus, and energy at break of the cured film obtained in Example 13. As a result, it can be seen that the film-like cured product made of the resin composite obtained in Example 13 shows excellent characteristics as compared with the UA101H alone cured product (Reference Example 3).

Example 14 7 g of "UA101H" was used as the active energy ray crosslinkable polymerizable compound, 0.14 g of "Irgacure 184" was used as the photopolymerization initiator, and "N200" (Ethyl cellulose manufactured by Hercules) was used as the thermoplastic resin. ) In methylene chloride / acetone (3 /
7) A homogeneous mixed solution (14) dissolved in 70 g of a mixed solvent
I got

A film was prepared in the same manner as in Example 1, except that the homogeneous mixed solution (14) was used in place of the homogeneous mixed solution (1), and the ultraviolet irradiation temperature was set to 80 ° C. Produced. The uncured excipient was colorless and transparent at room temperature or higher. The cured film was cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.3 to 0.7 μm could be observed. Further, the result of the solvent extraction test performed in the same manner as in Example 1 except that a methylene chloride / acetone (3/7) mixed solvent was used instead of methylene chloride in Example 1, the results were the same as in Example 1. there were.

Table 4 shows the measurement results of the strength, elongation at break, elastic modulus and energy at break of the cured film obtained in Example 14. As a result, it can be seen that the film-like cured product made of the resin composite obtained in Example 14 shows superior characteristics as compared with the UA101H alone cured product (Reference Example 3).

[0178]

[Table 4]

Example 15 As the active energy ray crosslinkable polymerizable compound, "urethane acrylate UA-30" was used.
6H "(Kyoeisha Chemical Co., Ltd. formula

[0180]

Embedded image

Hexaacrylate which is a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate represented by the following formula; hereinafter, referred to as “UA306H”
Is abbreviated. 7), 0.14 g of "Irgacure 184" as a photopolymerization initiator and a styrene-maleic anhydride copolymer (manufactured by Scientific Polymer Co .; hereinafter abbreviated as "SMAA") as a thermoplastic resin. 3 g was dissolved in 50 g of THF to obtain a homogeneous mixed solution (15).

After applying the homogeneous mixed solution (15) on a glass plate, the solvent was removed to obtain an uncured liquid film-like shaped product composed of the homogeneous mixed solution. This uncured liquid film-shaped excipient is at room temperature to
It was colorless and transparent at 80 ° C. While keeping at 80 ° C,
Two UV cut filters (Toshiba, UV-D36)
Using B), the liquid film-shaped shaped article was irradiated with ultraviolet rays whose ultraviolet intensity was reduced to 17 mW / cm ^{2, and} was cured. Further, in order to promote the reaction of the unreacted monomer in the coating film, the film was irradiated with the ultraviolet ray at 80 ° C., and the strength was 70% at room temperature.
Irradiation with ultraviolet light of mw / cm ² for 90 seconds gave a cured coating film (film thickness = about 120 μm).

The cured coating film thus obtained was colorless and transparent, and was in a good state without cracks. The light transmittance was 89%. When the TEM observation of the cross section of the coating film was performed, a network-like phase-separated structure having a diameter of 0.07 to 0.15 μm could be observed. Further, in Example 1, except that THF was used instead of methylene chloride,
The results of the solvent extraction test performed in the same manner as in Example 1 were the same as in Example 1. Furthermore, the surface hardness of the cured coating film is 6H
That was all.

[Comparative Example 5] The same procedure as in Example 15 was carried out except that the irradiation temperature of the ultraviolet light was lowered to 17 mW / cm ^2, and the irradiation temperature of the ultraviolet light was changed to room temperature (25 ° C). A membrane was made. The cured coating film was colorless and transparent, and was good without cracks. However, the surface hardness of the cured coating film was 4H, which was inferior to Example 15.

[Reference Example 4] In Example 15, no thermoplastic resin was used, no solvent was used, the glass plate cover was not attached, and the irradiation temperature was 25 ° C. Except for this, a film-like cured product of “UA306H” (film thickness = about 120 μm) was obtained in the same manner as in Example 15, but countless cracks were generated in the cured coating film. And a good coating film was not obtained.

Example 16 As an active energy ray crosslinkable polymerizable compound, "urethane acrylate UA-30" was used.
6T "" (Kyoeisha Chemical Co., Ltd. formula

[0187]

Embedded image

Hexaacrylate which is a reaction product of pentaerythritol triacrylate and tolylene diisocyanate represented by the following formula; hereinafter abbreviated as "UA306T". ) 7 g, "Irgacure 1" as a photopolymerization initiator
84 "as a thermoplastic resin and polyvinyl chloride (manufactured by Scientific Polymer Co., Ltd.) 3
g in 60 g of THF to obtain a homogeneous mixed solution (16).
I got

In Example 15, the homogeneous mixed solution (1
A film was produced in the same manner as in Example 15 except that the homogeneous mixed solution (16) was used instead of 5). The uncured excipient was colorless and transparent at room temperature or higher.

The cured coating film thus obtained was transparent, was free from cracks, and was in a good state. The light transmittance of the film was 87%. When the cross section of the coating film was observed by TEM, a network-like phase-separated structure having a diameter of 0.08 to 0.2 μm could be observed. Example 1
In the above, the result of the solvent extraction test carried out in the same manner as in Example 1 was the same as in Example 1, except that THF was used instead of methylene chloride. Further, the surface hardness of the cured coating film was 5H.

[Comparative Example 6] A cured coating film was obtained in the same manner as in Example 16, except that the irradiation temperature of the ultraviolet light was reduced to 17 mW / cm ² and the irradiation temperature was changed to room temperature (25 ° C). It was created. The cured coating film was colorless and transparent, and was good without cracks. However, the surface hardness of the cured coating film was 4H, which was inferior to that of Example 16.

[Reference Example 5] In Example 16, no thermoplastic resin was used, no solvent was used, no glass plate cover was attached, and the irradiation temperature was 25 ° C. Except for the above, a cured film of “UA306T” (film thickness = about 120 μm) was obtained in the same manner as in Example 16, but countless cracks occurred in the cured coating film. And a good coating film was not obtained.

Example 17 7 g of "UA-306T" was used as the active energy ray crosslinkable polymerizable compound, 0.14 g of "Irgacure 184" was used as the photopolymerization initiator, and polyvinyl acetate (Scientific) was used as the thermoplastic resin. 3 g of Polymer Co., Ltd.) was dissolved in 60 g of methylene chloride to obtain a homogeneous mixed solution (17).

In Example 15, the homogeneous mixed solution (1
A film was produced in the same manner as in Example 15 except that the homogeneous mixed solution (17) was used instead of 5). The uncured excipient was colorless and transparent at room temperature or higher.

The cured coating film thus obtained was colorless and transparent, and was in a good state without cracks. The light transmittance of the film was 90%. When the TEM observation of the cross section of the coating film was performed, a network-like phase-separated structure having a diameter of 0.07 to 0.2 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1. Further, the surface hardness of the cured coating film was 5H.

Example 18 The procedure of Example 17 was repeated, except that “Byron 500” (an aromatic polyester manufactured by Toyobo Co., Ltd.) was used instead of polyvinyl acetate. A mixed solution (18) was obtained.

In Example 15, the homogeneous mixed solution (1
A film was produced in the same manner as in Example 15 except that the homogeneous mixed solution (18) was used instead of 5). The uncured excipient was colorless and transparent at room temperature or higher.

The cured coating film thus obtained was colorless and transparent, and was in a good state without cracks. The light transmittance of the film was 89%. When the cross section of the coating film was observed by TEM, a network-like phase-separated structure having a diameter of 0.08 to 0.2 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1. Further, the surface hardness of the cured coating film was 5H.

Example 19 A homogeneous mixed solution (Example 19) was prepared in the same manner as in Example 17, except that polyvinyl formal (manufactured by Scientific Polymer Co., Ltd.) was used instead of polyvinyl acetate. 19) was obtained.

In Example 15, the homogeneous mixed solution (1
A film was produced in the same manner as in Example 15 except that the homogeneous mixed solution (19) was used instead of 5). The uncured excipient was colorless and transparent at room temperature or higher.

The cured coating film thus obtained was transparent and in a good condition without cracks. The light transmittance of the film was 87%. When the TEM observation of the cross section of the coating film was performed, a network-like phase-separated structure having a diameter of 0.06 to 0.15 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1. Further, the surface hardness of the cured coating film was 5H.

Example 20 In Example 17, "Pandex-T5205" was used in place of polyvinyl acetate.
A homogeneous mixed solution (20) was obtained in the same manner as in Example 17, except that (a thermoplastic polyurethane manufactured by Dainippon Ink and Chemicals, Inc.) was used.

In Example 15, the homogeneous mixed solution (1
A film was produced in the same manner as in Example 15 except that the homogeneous mixed solution (20) was used instead of 5). The uncured excipient was colorless and transparent at room temperature or higher.

The cured coating film thus obtained was colorless and transparent, and was in a good state without cracks. The light transmittance of the film was 90%. When the cross section of the coating film was observed by TEM, a network-like phase-separated structure having a diameter of 0.06 to 0.2 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1. Further, the surface hardness of the cured coating film was 4H.

Example 21 8 g of "UA-306T" was used as the active energy ray crosslinkable polymerizable compound, 0.16 g of "Irgacure 184" was used as the photopolymerization initiator, and "Nippol AR71" (Nippon Zeon) was used as the thermoplastic resin. 2 g of acrylic rubber (manufactured by the company) was dissolved in 70 g of methylene chloride to obtain a homogeneous mixed solution (21).

In Example 15, the homogeneous mixed solution (1
A film was produced in the same manner as in Example 15 except that the homogeneous mixed solution (21) was used instead of 5). The uncured excipient was colorless and transparent at room temperature or higher.

The cured coating film thus obtained was colorless and transparent, and was in a good state without cracks. The light transmittance of the film was 90%. When the TEM observation of the cross section of the coating film was performed, a network-like phase-separated structure having a diameter of 0.06 to 0.15 μm could be observed. The results of the solvent extraction test performed in the same manner as in Example 1 were the same as those in Example 1. Further, the surface hardness of the cured coating film was 5H.

[0208]

The resin composite of the present invention has improved mechanical properties as compared with a polymer composed of an active energy ray crosslinkable polymerizable compound, and is also optically transparent. Further, the resin composite of the present invention is superior in mechanical properties as compared with a resin composite showing one glass transition temperature. In addition, the method for producing a resin composite of the present invention has the advantages of high production stability, easy control of characteristics, little variation in product quality, and high productivity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 290/06 C08F 290/06 291/00 291/00 299/06 299/06 C08L 55/00 C08L 55 / 00 101/00 101/00 F term (reference) 4J002 AB01X AC02X BC02X BD03X BE06X BF02X BG07W BQ00W CF00X CG00X CH08X CK02X GH00 GJ02 4J011 PA53 PA54 PA65 PA66 PA67 PA68 PA88 PA89 PA90 PA95 PB40 PC02 PC08 QA03 QAQAA QAQA QA39 QA43 QA45 QA46 QB05 QB16 QB19 QB24 SA02 SA07 SA12 SA14 SA16 SA19 SA22 SA25 SA32 SA34 SA54 SA58 SA64 SA82 TA07 UA01 UA02 UA03 UA04 UA06 VA08 VA09 WA02 4J026 AA02 AA17 AA24 AB27 AB08 AB27 AB08 DB09 DB36 GA02 GA06 4J027 AA04 AC01 AC03 AC04 AC06 AE01 AG03 AG04 AG05 AG09 AG10 AG12 AG23 AG24 AG25 AG27 BA07 BA08 BA13 CA02 CA04 CA05 CA06 CA08 CA10 CB10 CC04 CC05 CC06 CC07 CC08 CD06 CD08 4J100 AL66P AL67P BA04P BA38P BA39P BC43P CA01 JA01

Claims (12)

[Claims] 1. A resin composite having a co-continuous structure comprising: (a) a crosslinked polymer which is a cured product of an active energy ray crosslinkable polymerizable compound; and (b) a thermoplastic resin. The active energy ray crosslinkable polymerizable compound is a urethane (meth) acrylate having 2 to 6 (meth) acryloyl groups in one molecule, and (2) the thermoplastic resin is a polycarbonate polymer or a polyester polymer. , Phenoxy resin, vinyl acetal polymer, vinyl chloride polymer, vinyl acetate polymer,
A resin composite comprising at least one thermoplastic resin selected from the group consisting of a styrene polymer, a urethane polymer, an uncrosslinked rubber, and a cellulose derivative. 2. The method according to claim 1, wherein the resin composite having a co-continuous structure is 0.1.
The resin composite according to claim 1, which has a thermoplastic resin phase having a network structure having a size in a range of 02 to 0.1 µm. 3. The resin composite having a bicontinuous structure has two glass transition temperatures (Tg).
Or the resin composite according to 2. 4. The method according to claim 1, wherein the urethane (meth) acrylate is 2-
Di (meth) acrylate which is a reaction product of hydroxy-3-phenoxypropyl (meth) acrylate and hexamethylene diisocyanate, wherein the thermoplastic resin is a polyester polymer, a phenoxy resin, a vinyl acetal polymer, or a vinyl chloride polymer. 2. The resin according to claim 1, which is at least one resin selected from the group consisting of polymers, vinyl acetate polymers, styrene polymers, urethane polymers and uncrosslinked rubber.
The resin composite according to any one of claims 1 to 3, wherein 5. The method according to claim 1, wherein the urethane (meth) acrylate is 2-
Di (meth) acrylate which is a reaction product of hydroxy-3-phenoxypropyl (meth) acrylate and tolylene diisocyanate, wherein the thermoplastic resin is a polycarbonate-based polymer, a polyester-based polymer, a phenoxy resin, a vinyl acetal-based polymer. The resin according to claim 1, wherein the resin is at least one resin selected from the group consisting of a coalescent, a vinyl chloride-based polymer, a vinyl acetate-based polymer, a styrene-based polymer, a urethane-based polymer, and an uncrosslinked rubber. Resin composite. 6. The urethane (meth) acrylate is tetra (meth) acrylate which is a reaction product of glycerol (meth) acrylate and hexamethylene diisocyanate, and the thermoplastic resin is a polyester polymer, a phenoxy resin, a vinyl acetal. At least one resin selected from the group consisting of a vinyl polymer, a vinyl acetate polymer, a vinyl chloride polymer, a styrene polymer, a urethane polymer, an uncrosslinked rubber, and a cellulose derivative.
The resin composite according to any one of the above. 7. The urethane (meth) acrylate is hexa (meth) acrylate which is a reaction product of pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate, and the thermoplastic resin is a vinyl acetal polymer, vinyl acetate The thermoplastic polymer is one or more thermoplastic resins selected from the group consisting of a series polymer, a styrene series polymer, a urethane series polymer, an uncrosslinked rubber and a cellulose derivative. Resin composite. 8. The urethane (meth) acrylate is hexa (meth) acrylate, which is a reaction product of pentaerythritol tri (meth) acrylate and tolylene diisocyanate, and the thermoplastic resin is a polyester-based polymer or a vinyl acetal-based resin. Polymer, vinyl chloride polymer,
4. One or more thermoplastic resins selected from the group consisting of vinyl acetate polymers, styrene polymers, urethane polymers, uncrosslinked rubbers and cellulose derivatives. Item 10. The resin composite according to item 8. 9. An active energy ray-curable urethane (meth) acrylate having 2 to 6 (meth) acryloyl groups in one molecule, and (2) a polycarbonate polymer, a polyester polymer, and phenoxy. From one or more thermoplastic resins selected from the group consisting of resins, vinyl acetal polymers, chlorine-containing vinyl polymers, vinyl acetate polymers, styrene polymers, urethane polymers, uncrosslinked rubbers and cellulose derivatives. 2. The method of claim 1, wherein after shaping the homogeneous mixture, the shaped article of the uniform mixture is cured by irradiating active energy rays to induce phase separation and fix the bicontinuous structure. A method for producing the resin composite according to the above. 10. A homogeneous mixed solution comprising (1) an active energy ray-curable urethane (meth) acrylate, (2) a thermoplastic resin, and (3) a solvent that dissolves the same, is shaped. The method for producing a resin composite according to claim 9, wherein the resin composite is dried and removed to form a shaped product of a uniform mixed solution, and then irradiated with an active energy ray. 11. The homogeneous mixture contains a photopolymerization initiator,
The method for producing a resin composite according to claim 9 or 10, wherein the active energy rays are ultraviolet rays. 12. An active energy ray irradiation temperature of 50 to 2
The method for producing a resin composite according to claim 9, 10 or 11, wherein the temperature is 00 ° C.