JP2001220515A - Resin composite having co-continuous structure and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composite which has mechanical characteristics better than those of a polymer formed from an active energy ray-crosslinkable and polymerizable compound, can be optically transparent, and has mechanical characteristics better than those of a resin composite exhibiting one glass transition point. SOLUTION: This resin composite, having a co-continuous structure, comprises (A) a crosslinked polymer which is a cured product of a polyester (meth)acrylate having 2-6 (meth)acrylate groups and (B) at least one thermoplastic resin selected from the group consisting of polyester polymers, phenoxy resins, vinyl acetal polymers, vinyl chloride polymers, vinyl acetate polymers, styrene polymers, unvulcanized rubbers, urethane polymers, and cellulose derivatives.

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. Impact resistance, a resin composite having excellent mechanical properties such as abrasion resistance, and a resin composite having excellent optical properties and optical transparency as well as the above-mentioned mechanical properties, and a method for producing the same. The present invention relates to a resin composite comprising a polymer and having a bicontinuous microphase separation structure 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.

[0004]

However, in the method disclosed in JP-A-11-80556, an amide polymerizable compound such as N, N-dimethylacrylamide must be used in combination in order to improve the affinity of the resin. Because
There has been a problem that the moisture absorption of the resin changes due to the atmospheric humidity, and the characteristics greatly change.

Further, since the resin composite described in the above-mentioned Japanese Patent Application Laid-Open No. 7-33991 is a pseudo-compatible system, the degree of improvement in the mechanical properties is at most limited to that of a cured product of a photosensitive resin and a 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.

[0006] Furthermore, the method described in the above-mentioned Japanese Patent Application Laid-Open No. 7-102175 discloses a method of using a polysulfone resin, which generally has a poor affinity for the photosensitive composition, as the thermoplastic resin. However, there is a problem that the resin is limited to a partially acrylated epoxy resin having a 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.

[0007]

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. The present inventors have found that a resin composite having improved mechanical properties can be stably produced by shaping and curing by irradiation with active energy rays, and at the same time, causing phase separation. Thus, the present invention has been achieved.

That is, in order to solve the above 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 polyester (meth) acrylate having 2 to 6 (meth) acryl groups in one molecule, (2) Thermoplastic resin, polyester polymer, phenoxy resin, vinyl acetal polymer,
A resin composite that is at least one thermoplastic resin selected from the group consisting of vinyl chloride-based polymers, vinyl acetate-based polymers, styrene-based polymers, uncrosslinked rubbers, urethane-based polymers, and cellulose derivatives. .

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 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 (IV) a polyester (meth) acrylate having 2 to 6 (meth) acrylic groups in one molecule, which is a hydroxybivalic acid ester neopentylglycol diester. (Meta)
Acrylate or caprolactone-modified dipentaerythritol hexa (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, or a styrene polymer. The present invention provides a resin composite having a co-continuous structure according to the above (I), (II) or (III), which is one or more thermoplastic resins selected from the group consisting of a united polymer, an uncrosslinked rubber, and a urethane-based polymer. I do.

In order to solve the above-mentioned problems, the present invention provides (V) a polyester (meth) acrylate having 2 to 6 (meth) acryl groups in one molecule, wherein caprolactone-modified hydroxybivalic acid ester neopentyl is used. Glycol di (meth) acrylate, wherein the thermoplastic resin is a polyester polymer, phenoxy resin, vinyl acetal polymer, vinyl chloride polymer, vinyl acetate polymer, styrene polymer, uncrosslinked rubber, urethane A resin composite having a co-continuous structure according to the above (I), (II), (III) or (IV), which is at least one thermoplastic resin selected from the group consisting of a base polymer and a cellulose derivative. I do.

In order to solve the above-mentioned problems, the present invention provides (VI) (1) an active energy ray-curable polyester (meth) acrylate having 2 to 6 (meth) acryl groups in one molecule, and (2) from the group consisting of polyester polymers, phenoxy resins, vinyl acetal polymers, chlorine-containing polymers, vinyl acetate polymers, styrene polymers, uncrosslinked rubbers, urethane polymers, and cellulose derivatives After shaping a uniform mixture of at least one selected thermoplastic resin, the mixture is irradiated with active energy rays,
The method for producing a resin composite according to any one of the above (I) to (V), which induces phase separation and fixes a bicontinuous structure.

Furthermore, the present invention has been made to solve the above-mentioned problems by providing (VII) (1) an active energy ray-curable polyester (meth) acrylate, (2) a thermoplastic resin,
(3) The resin composite according to the above (VI), wherein after shaping a homogeneous mixed solution comprising a solvent that dissolves these, the solvent is dried and removed, and thereafter, an active energy ray is irradiated. And a method for producing the same.

Further, in order to solve the above problems, the present invention provides (VIII) a homogeneous mixture containing a photopolymerization initiator,
(VI) or (VI) wherein the active energy ray is ultraviolet light.
A method for producing the resin composite according to the item (I) is provided.

In order to solve the above-mentioned problems, the present invention provides (IX) an active energy ray irradiation temperature of 50 to 20.
A method for producing the resin composite according to the above (VI), (VII) or (VIII), wherein the method is at 0 ° C.

[0017]

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”). A certain crosslinked polymer ”may be referred to as an“ active energy ray crosslinked polymer ”). The resin composite of the present invention has a phase having a relatively high thermoplastic resin concentration (hereinafter, referred to as a thermoplastic resin phase).
And a resin composite microphase-separated into a phase having a relatively high active energy ray crosslinked polymer concentration (hereinafter referred to as a crosslinked polymer phase), and each phase is three-dimensionally continuous. It has a structure, that is, a bicontinuous structure. In a cross section in any direction of the resin composite of the present invention observed by a transmission electron microscope (TEM), a thermoplastic resin phase continuous in a network can be observed. The mesh may have partially broken portions. On the other hand, in a cross-sectional observation using a transmission electron microscope, the crosslinked polymer phase may be observed as an independent cell surrounded by a thermoplastic phase. However, even when the resin composite of the present invention is immersed in a solvent that dissolves a thermoplastic resin, the crosslinked polymer phase does not decompose into powder. When a cross section of the resin composite washed with a solvent that dissolves a thermoplastic resin is observed with a scanning electron microscope (SEM), a structure in which particles are connected to each other can be observed.

From these facts, in the resin composite of the present invention, almost spherical cells composed of a crosslinked polymer phase are almost wrapped by a thermoplastic resin phase which is a continuous three-dimensional network phase. However, it is thought that the cells are not completely wrapped and adopt a structure where 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 two glass transition temperatures between the glass transition temperature TgC of the crosslinked polymer constituting the resin composite and the glass transition temperature TgL of the thermoplastic resin constituting the resin composite. Tg1 and Tg2 (however, Tg
1 <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, Tg
C <TgL or TgC> TgL. However, when TgC <TgL, Tg1 ≦ T
gC. Also, TgC = TgL (TgC
(Including TgL), the two glass transition temperatures degenerate, and even if the resin composite according to the present invention has a Tg of 2
Cannot be determined. 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 measuring method, for example, dynamic viscoelasticity, differential calorimetry (DSC) and the like. 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, indicates that the polymer constituting the resin composite is phase-separated, Generally, the mechanical properties of the resin composite may be higher than those of the (pseudo) compatible system,
It is known that it may be lower and may vary greatly depending on the shape of the phase separation. Optically, usually,
It is 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 molded into a molded article of any 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 crosslinked polymer constituting the resin composite of the present invention is a crosslinked polymer obtained by curing an active energy ray crosslinkable polymerizable compound by irradiation with active energy rays, that is, an active energy ray crosslinked polymer.

The active energy ray-crosslinkable polymerizable compound used in the present invention is a polyester (meth) acrylate having 2 to 6 (meth) acryl groups in one molecule.
These polyester (meth) acrylates may be those that are cured by active energy rays only in the presence of a photopolymerization initiator. The active energy ray crosslinkable curable compound may be used alone, or two or more kinds of the polyester (meth) acrylates may be mixed with each other or with another type of active energy ray crosslinkable polymerizable compound.

The polyester (meth) acrylate having 2 to 6 (meth) acryl groups in one molecule is preferably a polyhydric alcohol having one or more, preferably a plurality of ester bonds in the skeleton (hereinafter referred to as “one or more preferably Is a "polyhydric alcohol having a plurality of ester bonds in the skeleton" may be referred to as "polyester polyol")) (meth) acrylic acid ester, the polyester skeleton of the polyester polyol is a linear or branched polyester And may be a substituted polyester. The polyester polyol can be, for example, a reaction product of a polybasic acid compound or an anhydride thereof and a polyol.

Examples of the polybasic acid compound or its anhydride as a raw material of the polyester polyol include maleic acid, succinic acid, adipic acid, isophthalic acid, phthalic acid,
And terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and anhydrides thereof. Also,
Similarly, examples of the polyols include ethylene glycol, propylene glycol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, and pentaerythritol.

By using such a polyester (meth) acrylate as an active energy ray crosslinkable polymerizable compound, a resin composite having a bicontinuous structure can be easily obtained, and high mechanical properties can be realized. .

As the polyester (meth) acrylate, for example, a compound represented by the general formula

[0032]

Embedded image

(In the formula, -X represents a hydrogen atom or a methyl group, and R ¹ represents an arbitrary divalent group having carbon atoms at both ends. When i is zero, an ester bond is provided in the middle. R ² is any divalent group having both ends carbon.
(Wherein, n represents a positive integer.) In formula -C _n H _2n COO- represents a divalent group or a substitution product thereof represented by.
i is zero or a positive integer, and j is i + j from 0 to 6
This value satisfies the range. )).

In the general formula (I), R¹ Is in the middle
An arbitrary divalent group having carbon atoms at both ends having a stele bond
Preferably, R¹ Is -CH_TwoC (CH_Three)_TwoCOOCH_TwoC (CH
_Three)_TwoCH_Two-Is particularly preferred. Also, the general formula
In (I), R^Two Is -C_FiveH _TenCOO−
preferable. Furthermore, i + j is 0, 2, or 4.
Is preferred.

The polyester (meth) acrylate having six (meth) acryl groups in one molecule includes, for example, a compound represented by the following general formula (2)

[0036]

Embedded image

(In the formula, -X represents a hydrogen atom or a methyl group, and R ³ represents a general formula-(COC _k H _2k O) _m-
Represents an integer of 2 to 6, and m represents an integer of 1 to 3. ) Represents a divalent group. a, b, c,
d, e and f each represent zero or a positive integer, where a + b + c + d + e + f is in the range of 0-15. )).

In the general formula (2), R ³ is —COC ₅ H
It is preferably ₁₀ O- or-(COC ₅ H ₁₀ O) _2- . Further, a + b + c + d + e + f is preferably 2, 3, 6, or 12.

In order to control the properties of the resin composite, the active energy ray-crosslinkable polymer is mixed with an active energy ray-crosslinkable polymerizable compound, which alone does not give a crosslinked polymer. It may be a copolymer with a compound having a polymerizable functional group (hereinafter, referred to as a monofunctional active energy ray polymerizable compound).

Examples of the monofunctional (meth) acrylic monomer that can be used for such a purpose include 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) ) Acrylates, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydrido Propyl acrylate, ethylene oxide-modified phthalic acid acrylate, .omega. alkoxy monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid, acrylic acid dimer, 2
-Acryloyloxypropyl hexahydrohydrogen phthalate, fluorine-substituted alkyl (meth) acrylate, chlorine-substituted alkyl (meth) acrylate, sodium sulfonic acid (meth) acrylate, (meth) acrylate having a phosphate group, and silanol group ( (Meth) acrylate, (meth) acrylate having a dialkylamino group, and the like.

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 is preferably one which is uniformly mixed with the active energy ray crosslinkable polymerizable compound used in the present invention, preferably at a temperature of 200 ° C. or less, and is a polyester-based polymer, a phenoxy resin. And a thermoplastic resin selected from the group consisting of vinyl acetal polymers, vinyl chloride polymers, vinyl acetate polymers, styrene polymers, uncrosslinked rubbers, urethane polymers and cellulose derivatives. 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 is easily formed, and properties are easily improved. 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, those having a melting point of 200 ° C. or lower are preferable, and those having a melting point of 100 ° C. or lower are particularly preferable.
Those having a high melting point of the crystalline polymer used as the thermoplastic resin are not preferred at a temperature of 200 ° C. or lower, because the compatibility with the active energy ray crosslinkable polymerizable compound tends to be poor.

The polyester polymer which can be used in the present invention is a condensation polymer of a polycarboxylic acid and a polyhydric alcohol,
Copolymers and their substituted products are exemplified.

The polyhydric alcohol constituting the polyester polymer usable in the present invention includes, for example, bisphenol-A, bisphenol-F, bisphenol-
Z, tetramethylbiphenol, ethylene glycol,
Propylene glycol, butylene glycol, pentanediol, hexamethylene glycol, octanediol, neopentyl glycol, cyclohexanediol, diethylene glycol, triethylene glycol,
Examples thereof include dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. These polyhydric alcohols can be used in combination of two or more. Among these polyhydric alcohols, ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol,
Neopentyl glycol is particularly preferred.

Examples of the polycarboxylic acid constituting the polyester polymer usable in the present invention include aromatic carboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; succinic acid, adipic acid, azelaic acid, sebacine Aliphatic dicarboxylic acids having 4 to 14 carbon atoms such as acids, brassic acid, cyclohexanedicarboxylic acid;
Examples thereof include dimer acid, trimellitic acid, pyromellitic acid, trimellitic anhydride, and pyromellitic anhydride. Two or more of these polycarboxylic acids can be used in combination. Among these polycarboxylic acids, 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.

The vinyl acetal polymer usable in the present invention includes, for example, polyvinyl formal and polyvinyl acetal.

The vinyl chloride polymer usable in the present invention includes, for example, vinyl chloride, chlorinated polyethylene, chlorinated polypropylene and the like. The chlorinated polyethylene and the chlorinated polypropylene are preferably high-chlorinated polymers having a chlorine content of 50% or more.

Examples of the vinyl acetate polymer that can be used in the present invention include polyvinyl acetate, ethylene-vinyl acetate copolymer (EVA), and the like.

Examples of the styrene polymer usable in the present invention include polystyrene (PS), polyα-methylstyrene, styrene-methyl methacrylate copolymer (MS), and styrene-acrylonitrile copolymer (A
S), styrene-maleic anhydride copolymer (SMA)
A), a styrene-maleic acid copolymer, and the like.

The urethane polymers used 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.
Polymerization of isocyanates such as dicyclohexylmethane diisocyanate with 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 which is a product. Among these urethane polymers,
Urethane polymers using tolylene diisocyanate or diphenylmethane diisocyanate as the isocyanate and polyester polyols of 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and adipic acid as the polyol are preferred.

Examples of the uncrosslinked rubber which can be preferably used in the present invention include diene rubbers such as butadiene rubber (BR), acrylonitrilo-butadiene rubber (NBR) and styrene-butadiene rubber (SBR); chloroprene rubber, isoprene rubber and the like. And an acrylic rubber (AR). Among these uncrosslinked rubbers, NBR, SBR and AR are particularly preferred.

Examples of the cellulose derivative that can be preferably used in the present invention include organic acid celluloses such as cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate; methylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, ethylcellulose and ethylcellulose. Cellulose ethers such as hydroxyethylcellulose, hydroxyethylcellulose, carboxymethylhydroxyethylcellulose, sodium carboxymethylcellulose, and hydroxypropylcellulose; and inorganic celluloses such as nitrocellulose, cellulose sulfate, and cellulose phosphate. Among these cellulose derivatives, ethyl cellulose and nitrocellulose are particularly preferred.

Among the thermoplastic resins, polyether sulfone and polysulfone have 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. For example, (1) an active energy ray crosslinkable polymerizable compound selected from the group consisting of (1-a) hydroxybivalic acid ester neopentyl glycol di (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate; 1-b) Heat selected from the group consisting of polyester polymers, phenoxy resins, vinyl acetal polymers, vinyl chloride polymers, vinyl acetate polymers, styrene polymers, uncrosslinked rubbers and urethane polymers A combination with a plastic resin,

(2) (2-a) Caprolactone-modified hydroxybivalic acid ester neopentyl glycol di (meth) acrylate and (2-b) polyester polymer, phenoxy resin, vinyl acetal polymer, vinyl chloride A combination with a thermoplastic resin selected from the group consisting of a polymer, a vinyl acetate polymer, a styrene polymer, an uncrosslinked rubber, a urethane polymer and a cellulose derivative is particularly preferred.

The composition ratio between the active energy ray crosslinked polymer and the thermoplastic resin varies depending on the type of resin used, but usually the weight ratio of (active energy ray crosslinked polymer: thermoplastic resin) is (98: 2). To (10:90) is preferable, and the range of (95: 5) to (20:80) is particularly preferable.

According to the resin composite of the present invention, it is possible to obtain a composite having excellent mechanical properties such as imparting both flexibility and toughness which are characteristics of a thermoplastic resin. Depending on the type of the thermoplastic resin, characteristics of the resin are given. For example, in an aromatic polyester polymer or a vinyl chloride polymer, a high elastic modulus can be effectively imparted, and in a polycarbonate, a urethane polymer, a vinyl acetate polymer, or an uncrosslinked rubber, Elongation at break, impact resistance and the like can be effectively imparted, and phenoxy resin and cellulose derivatives can effectively impart high surface affinity and the like.

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; thermosetting resins such as epoxy resins; antifungal agents; antibacterial agents; Powder; reinforcing fibers and the like can be contained in a mixed or copolymerized form. Further, the resin composite of the present invention may be 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, an active energy beam crosslinkable polymerizable compound and a thermoplastic resin are mixed to prepare a homogeneous mixed solution (hereinafter, this homogeneous mixed solution may be simply referred to as “homogeneous mixed solution”). . After shaping the homogeneous mixed solution, a method of irradiating active energy rays to cure the shaped product of the uniform mixed solution to induce phase separation and to fix the bicontinuous structure.

The active energy ray-crosslinkable polymerizable compound used in the production method of the present invention is a polyester (meth) acrylate having 2 to 6 (meth) acryl groups in one molecule. It is possible to form a uniform mixture with the plastic resin. The active energy ray crosslinkable polymerizable compound used in the production method of the present invention is the same as the description of the active energy ray crosslinkable polymerizable compound that can be used for the resin composite of the present invention.

The thermoplastic resin used in the production method of the present invention includes a polyester polymer, a phenoxy resin, a vinyl acetal polymer, a vinyl chloride polymer, a vinyl acetate polymer, a styrene polymer, and an uncrosslinked rubber. , A thermoplastic resin selected from the group consisting of a urethane polymer and a cellulose derivative, preferably capable of forming a homogeneous mixture with the active energy ray crosslinkable polymerizable compound to be used at a temperature of 200 ° C. or lower. It is. 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 the active energy ray crosslinkable polymerizable compound and the thermoplastic resin are uniformly mixed. However, it is permissible that a very small amount of an insoluble portion due to, for example, the molecular weight distribution of the chain polymer is present.

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 cp.
It is preferably in the range of ^{s (10 -3 ~10 2 Pa ·} s), 5~
A range of 100,000 cps (5 × 10 ^{−2 to} 10 Pa · s) is particularly preferable.

The homogeneous mixture 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, or the like. UV absorbers; antioxidants; inorganic or organic powders; reinforcing fibers;

The monofunctional active energy ray-polymerizable compound alone does not give a crosslinked polymer, but may be one which gives a crosslinked polymer by copolymerizing with the active energy ray-crosslinkable polymerizable compound by irradiation with active energy rays. Is optional,
This is the same as the description of the monofunctional active energy ray polymerizable compound that can be used in the resin composition of the present invention. By adding the monofunctional active energy ray polymerizable compound, the compatibility between the active energy ray crosslinkable polymerizable compound and the thermoplastic resin can be increased, and the reactivity of the homogeneous mixture can be controlled.

When a light ray such as an ultraviolet ray, a visible light ray or an infrared ray 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.

Examples of such a photopolymerization initiator include, for example, p-tert-butyltrichloroacetophenone,
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; and benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone.

The photopolymerization initiator can be used in the state of being dissolved or dispersed in a homogeneous mixed solution, but is preferably one which is dissolved in the homogeneous mixed solution. 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.

[0075] ? ? The homogeneous mixture is preferably from 0 to 20.
It is prepared in a temperature range of 0 ° C, more preferably 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 a 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. The volatile solvent has a boiling point of 150 ° C.
The following are preferable, and those having a boiling point of 120 ° C. or lower are particularly preferable.

Examples of such a solvent include: chlorinated 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; diethyl. Ether solvents such as ether, dibutyl ether and tetrahydrofuran; hydrocarbon solvents such as toluene and cyclohexane; organic acids such as formic acid; phenols such as chlorophenol; liquefied gases such as liquefied carbon dioxide and liquefied ammonia; And other supercritical fluids.

Although the method of removing the solvent is optional, 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 uniform liquid 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 mixture 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.

Further, in order to increase the curing speed and complete the curing, it is preferable to perform 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.

[0085]

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 light source. UV irradiation intensity is about 70mW / c
m ² . The ultraviolet irradiation time was 90 seconds.

Next, a method for measuring a glass transition temperature, a method for a tensile fracture test, a method for measuring a light transmittance, and a method for 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 measuring 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 0.15m
The test was performed with a sample length of 10 mm and a tensile speed of 5 mm / min.

(Measurement of Light Transmittance) Using a turbidimeter “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 by 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, "Kayarad MANDA" (hydroxybivalate ester neopentyl glycol diacrylate manufactured by Nippon Kayaku Co., Ltd .; hereinafter abbreviated as "MANDA") 5 g, 0.1 g of "Irgacure 184" (1-hydroxycyclohexyl phenyl ketone manufactured by Ciba Geigy) as a photopolymerization initiator and 5 g of "PKHH" (phenoxy resin manufactured by Union Carbide) as a thermoplastic resin. It was dissolved in 50 g of tetrahydrofuran (hereinafter abbreviated as "THF") 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 a coating film of the homogeneous mixed solution. Next, a cover of a glass plate was closely attached to the coating film, and an uncured shaped product 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 became cloudy at room temperature (25 ° C.), but became colorless and transparent at 50 ° C. or higher. The cross-linked polymerizable compound was polymerized by irradiating ultraviolet rays while keeping the shaped article at 100 ° C., and the shaped article was cured.

A film (film thickness = about 150 μm) obtained by peeling the obtained cured product from a glass plate was transparent at room temperature,
The light transmittance of the coating film was 88%. The Tg of this film was measured and found to be 2 t at 72 ° C. and 88 ° C.
An an δ peak could be observed. When the cross section of the film was observed using a TEM, the size of the diameter was 30 to 5
A network-like phase separation structure of 0 nm could be observed. Further, when the film was immersed in THF for 1 hour, no change was observed in the shape of the film. Furthermore, the eluate 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).
Substantially no particles were found.

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 is significantly improved in any of the evaluation items as compared with the cured products of Reference Example 1 and Comparative Example 1 described below. I understand.

Comparative Example 1 The uncured shaped product prepared in Example 1 was sandwiched between two glass plates and heated to 50 ° C. on a temperature-regulated stage. Later, 2
Cooled to 5 ° C. After cooling to 25 ° C., and after an elapse of 10 minutes, the crosslinked polymerizable compound was polymerized by irradiating ultraviolet rays to cure the excipient. The uncured shaped material cooled from 50 ° C. to 25 ° C. was kept in a transparent state for 4 hours or more.

A film (thickness = about 100 μm) obtained by peeling the obtained cured product from the glass plate was colorless and transparent at room temperature. When the Tg of this film was measured,
One tan δ peak could be observed around 0 ° C. 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, in the same manner as in Example 1, a film-shaped cured product of MANDA alone (film thickness = about 1
50 μm). 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 8 g of MANDA as an active energy ray crosslinkable polymerizable compound, 0.16 g of "Irgacure 184" as a photopolymerization initiator, and polyvinyl acetate as a thermoplastic resin (Scientific Polymer Co., Ltd.) (Mw = about 260,000) was dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (2).

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (2) was used in place of the homogeneous mixed solution (1), and that the UV irradiation temperature was 80 ° C. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and milky white.

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. Also, the result of the solvent extraction test performed in the same manner as in Example 1 was the same as that in Example 1, except that methylene chloride was used instead of THF.

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, it is understood that the cured film obtained from the resin composite obtained in Example 2 has a remarkably improved elongation at break and a significantly improved toughness.

Example 3 Example 2 was repeated, except that 2 g of “Pandex T5205” (polyurethane manufactured by Dainippon Ink and Chemicals, Inc.) was used in place of polyvinyl acetate. Thus, a homogeneous mixed solution (3) was obtained.

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (3) was used in place of the homogeneous mixed solution (1) and the ultraviolet irradiation temperature was 80 ° C. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and milky white.

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. Also, the result of the solvent extraction test performed in the same manner as in Example 1 was the same as that in Example 1, except that methylene chloride was used instead of THF.

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, it can be seen that the cured film obtained from the resin composite obtained in Example 3 has significantly improved elongation at break and significantly improved toughness.

Example 4 In Example 2, “Supercron HE-505” was used instead of polyvinyl acetate.
A homogeneous mixed solution (4) was obtained in the same manner as in Example 2 except that 2 g of (chlorinated polyethylene manufactured by Nippon Paper Industries Co., Ltd.) was used.

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (4) was used instead of the homogeneous mixed solution (1), and that the ultraviolet irradiation temperature was 60 ° C. The uncured excipient was colorless and transparent at room temperature to 60 ° C., but the cured film was thin and milky white.

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. Also, the result of the solvent extraction test performed in the same manner as in Example 1 was the same as that in Example 1, except that methylene chloride was used instead of THF.

The strength of the cured film obtained in Example 4
Table 1 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 cured film made of the resin composite obtained in Example 4 has greatly improved strength and elastic modulus.

[Example 5] In Example 2, a styrene-acrylonitrile copolymer (manufactured by Scientific Polymer Co., Ltd., Mw =
A homogeneous mixed solution (5) was prepared in the same manner as in Example 2 except that 2 g of a copolymer of 165,000 and the proportion of acrylonitrile in all the monomers constituting the copolymer were used (32%).
I got

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 60 ° C. The uncured excipient was colorless and transparent at room temperature to 60 ° C., but the cured film was thin and milky white.

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. Also, the result of the solvent extraction test performed in the same manner as in Example 1 was the same as that in Example 1, except that methylene chloride was used instead of THF.

The strength of the cured film obtained in Example 5
Table 1 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 cured film made of the resin composite obtained in Example 5 has greatly improved strength and elastic modulus.

Comparative Example 2 A cured film was obtained in the same manner as in Example 2 except that the ultraviolet irradiation temperature was changed to room temperature (25 ° C.). This cured film was colorless and transparent. About this film, TE
As a result of M observation, no phase-separated structure could be confirmed.

The strength of the cured film obtained in Comparative Example 2
Table 1 shows the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, it is understood that the cured film in Comparative Example 2 has low strength and low elongation at break.

Comparative Example 3 A cured film was obtained in the same manner as in Example 4, except that the ultraviolet irradiation temperature was changed to room temperature (25 ° C.). This cured film was colorless and transparent. About this film, TE
As a result of M observation, no phase-separated structure could be confirmed.

The strength of the cured film obtained in Comparative Example 3
Table 1 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 cured film of Comparative Example 3 has low strength, elastic modulus and elongation at break.

[0120]

[Table 1]

Example 6 As an active energy ray crosslinkable polymerizable compound, "Kayarad HX-220" (caprolactone-modified hydroxybivalate neopentyl glycol diacrylate manufactured by Nippon Kayaku Co., Ltd.) 8
g, "Irgacure 184" as a photopolymerization initiator.
Polyvinyl acetate (manufactured by Scientific Polymer Co., Ltd .; Mw = about 26
2 g) was dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (6).

A film was prepared 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 ultraviolet irradiation temperature was 60 ° C. The uncured excipient was colorless and transparent at room temperature to 60 ° C., but the cured film was thin and milky white.

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. Also, the result of the solvent extraction test performed in the same manner as in Example 1 was the same as that in Example 1, except that methylene chloride was used instead of THF.

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, it can be seen that the cured film obtained from the resin composite obtained in Example 6 has significantly improved strength, elastic modulus, and elongation at break.

Example 7 In Example 6, 2 g of polyvinyl chloride (Mn = 1100, manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of polyvinyl acetate, and 50 g of THF was used instead of methylene chloride. Except for the above, a homogeneous mixed solution (7) was obtained in the same manner as in Example 6.

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 the irradiation temperature of ultraviolet rays was set at 80 ° C. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and milky white.

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. The results of the solvent extraction test performed in the same manner as in Example 1 were also the same as 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, it can be seen that the cured film obtained from the resin composite obtained in Example 7 has significantly improved strength, elastic modulus and elongation at break.

[Example 8] In Example 6, styrene-acrylonitrile copolymer (manufactured by Scientific Polymer Co., Ltd., Mw =
A homogeneous mixed solution (8) was prepared in the same manner as in Example 6, except that 2 g of a copolymer of 165,000 and the proportion of acrylonitrile in all the monomers constituting the copolymer were used (32%).
I got

A film was produced 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 the ultraviolet irradiation temperature was 60 ° C. The uncured excipient was colorless and transparent at room temperature to 60 ° C., but the cured film was thin and milky white.

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. Also, the result of the solvent extraction test performed in the same manner as in Example 1 was the same as that in Example 1, except that methylene chloride was used instead of THF.

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, it can be seen that the cured film made of the resin composite obtained in Example 8 has significantly improved strength, elastic modulus, and elongation at break.

Example 9 The procedure of Example 6 was repeated, except that 2 g of “PKHH” was used instead of polyvinyl acetate, and 50 g of THF was used instead of methylene chloride. Solution (9) was obtained.

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 the ultraviolet irradiation temperature was 80 ° C. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and milky white.

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 also the same as 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, it can be seen that the cured film made of the resin composite obtained in Example 9 has significantly improved strength, elastic modulus and elongation at break.

Example 10 In Example 6, 2 g of "N-200" (ethyl cellulose manufactured by Hercules Co., Ltd.) was used instead of polyvinyl acetate, and acetone: methylene chloride = 7 was used instead of methylene chloride. 3 (capacity ratio)
A homogeneous mixed solution (10) was obtained in the same manner as in Example 6, except that 50 g of the mixed solvent was used.

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 the irradiation temperature of ultraviolet rays was 80 ° C. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and milky white.

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 except that a mixed solvent of acetone: methylene chloride = 7: 3 (volume ratio) was used instead of THF was also used. Example 1
Was similar to

Table 2 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 cured film made of the resin composite obtained in Example 10 has significantly improved strength, elastic modulus, and elongation at break.

Example 11 As an active energy ray crosslinkable polymerizable compound, 7 g of “Kayarad HX-220” was used.
As a photopolymerization initiator, “Irgacure 184” 0.14
As a thermoplastic resin, 3 g of "Byron-200" (aromatic polyester manufactured by Toyobo Co., Ltd.) was dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (11).

A film was produced 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 ultraviolet irradiation temperature was 80 ° C. The uncured excipient was cloudy at room temperature, but was colorless and transparent at 80 ° C. Further, the cured film was thin and milky cloudy.

When this film was observed with a TEM, a network-like phase-separated structure having a diameter of 0.1 to 0.4 μm could be observed. Also, the result of the solvent extraction test performed in the same manner as in Example 1 except that methylene chloride was used instead of THF was the same as that in Example 1.

Table 2 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, it can be seen that the cured film made of the resin composite obtained in Example 11 has greatly improved strength, elastic modulus, and elongation at break.

Comparative Example 4 A cured film was obtained in the same manner as in Example 6, except that the ultraviolet irradiation temperature was changed to room temperature (25 ° C.). This cured film was colorless and transparent. About this film, TE
As a result of M observation, no phase-separated structure could be confirmed.

The strength of the cured film obtained in Comparative 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 is found that the cured film in Comparative Example 4 is significantly inferior in strength and elastic modulus to the cured film in Example 6.

[Reference Example 2] In Example 6, 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, in the same manner as in Example 6, a film-shaped MANDA alone cured product (film thickness = about 1
50 μm). Table 2 shows the measurement results of the strength, breaking elongation, elastic modulus, and breaking energy of the cured film obtained in Reference Example 2.

[0148]

[Table 2]

Example 12 5 g of "Kayarad DPCA-60" (caprolactone-modified dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.) was used as an active energy ray crosslinkable polymerizable compound, and "Irgacure 184" was used as a photopolymerization initiator. 0.1 g and 5 g of "PKHH" as a thermoplastic resin were dissolved in 50 g of 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 instead of the homogeneous mixed solution (1). The uncured excipient was colorless and transparent at room temperature to 100 ° C., and the cured film was colorless and transparent (light transmittance = 90%).

When the Tg of this film was measured,
Two tan δ peaks could be observed at around 5 ° C. and 82 ° C. When the 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 performed in the same manner as in Example 1 were also the same as in Example 1.

Table 3 shows the measurement results of the strength, elongation at break, modulus of elasticity, and energy at break of the cured film obtained in Example 12. As a result, it can be seen that the cured film made of the resin composite obtained in Example 12 has significantly improved strength, elastic modulus, and elongation at break.

[Thirteenth Embodiment] In the twelfth embodiment, “Kayarad DPCA-60” and “Irgacure 184” are used.
And “PKHH” were used in amounts of 8 g and 1.6, respectively.
A homogeneous mixed solution (13) was obtained in the same manner as in Example 12, except that g and 2 g were used.

A film was produced 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 ultraviolet irradiation temperature was 80 ° C. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and milky white.

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 also 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 13. As a result, it can be seen that the cured film made of the resin composite obtained in Example 13 has significantly improved strength, elastic modulus, and elongation at break.

Example 14 As the active energy ray crosslinkable polymerizable compound, "Kayarad DPCA-60" 8
g, "Irgacure 184" as a photopolymerization initiator.
2 g of polyvinyl chloride (manufactured by Wako Pure Chemical Industries, Ltd., Mn = 1100) as a thermoplastic resin in THF 50
g) to obtain a homogeneous mixed solution (14).

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 irradiation temperature of ultraviolet rays was 80 ° C. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and milky white.

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 also the same as in Example 1.

Table 3 shows the results of measurement of the strength, elongation at break, modulus of elasticity and energy at break of the cured film obtained in Example 14. As a result, it can be seen that the cured film made of the resin composite obtained in Example 14 has significantly improved strength, elastic modulus and elongation at break.

[Example 15] In Example 14, “Pandex T5205” 2 was used in place of polyvinyl chloride.
g of the mixed solution (1) in the same manner as in Example 14 except that 50 g of methylene chloride was used instead of THF.
5) was obtained.

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (15) was used instead of the homogeneous mixed solution (1), and that the ultraviolet irradiation temperature was 80 ° C. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and milky white.

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. Moreover, the result of the solvent extraction test performed in the same manner as in Example 1 except that methylene chloride was used instead of THF was the same as that 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 15. As a result, it can be seen that the cured film obtained from the resin composite obtained in Example 15 has greatly improved strength, elastic modulus, and elongation at break.

Example 16 In Example 14, a styrene-maleic anhydride copolymer (Mw manufactured by Scientific Polymer Co., Ltd.) was used in place of polyvinyl chloride.
= 50,000, a homogeneous mixed solution (16) was obtained in the same manner as in Example 14, except that 2 g of the copolymer and the proportion of styrene in all the monomers constituting the copolymer were used (50%).

A film was prepared in the same manner as in Example 1 except that the homogeneous mixed solution (16) was used in place of the homogeneous mixed solution (1) and the ultraviolet irradiation temperature was 80 ° C. The uncured excipient was colorless and transparent at room temperature to 80 ° C., but the cured film was thin and milky white.

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.

Table 3 shows the measurement results of the strength, breaking elongation, elastic modulus and breaking energy of the cured film obtained in Example 16. As a result, it can be seen that the cured film obtained from the resin composite obtained in Example 16 has significantly improved strength, elastic modulus and elongation at break.

Comparative Example 5 A cured film was obtained in the same manner as in Example 12, except that the ultraviolet irradiation temperature was changed to room temperature (25 ° C.). When the Tg of this film was measured, one tan δ peak was observed at around 66 ° C., and it was presumed that the film was in a (pseudo) compatible state. The cured film was colorless and transparent. When a TEM observation was performed on this film, no phase-separated structure could be confirmed.

The strength of the cured film obtained in Comparative Example 5
Table 3 summarizes the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, although the cured film of Comparative Example 4 has improved properties as compared with the single cured product of DPCA-60 of Reference Example 3 described later, the cured product of Comparative Example 4 has the same properties as the cured film of Example 12. Thus, it can be seen that the characteristics are significantly inferior.

Comparative Example 6 A cured film was obtained in the same manner as in Example 12, except that the irradiation temperature of the ultraviolet ray was changed to room temperature (25 ° C.). This cured film was colorless and transparent. About this film,
As a result of TEM observation, no phase-separated structure could be confirmed.

The strength of the cured film obtained in Comparative Example 6
Table 3 summarizes the measurement results of the elongation at break, the elastic modulus, and the energy at break. As a result, although the film-form cured product of Comparative Example 6 had improved properties as compared with the single cured product of DPCA-60 of Reference Example 3 to be described later, the film-form cured product obtained in Example 12 Thus, it can be seen that the characteristics are significantly inferior.

[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. Except for the above, a film-like cured product of DPCA-60 alone (film thickness = about 150 μm) was obtained in the same manner as in Example 12. Table 3 shows the measurement results of the strength, breaking elongation, elastic modulus, and breaking energy of the film-shaped cured product obtained in Reference Example 3.

[0174]

[Table 3]

Example 17 6 g of "Kayarad DPCA-20" (caprolactone-modified dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.) as an active energy ray crosslinkable polymerizable compound and "Irgacure 184" as a photopolymerization initiator 0.12 g and 4 g of polyvinyl acetate (manufactured by Scientific Polymer Co., Ltd .; Mw = about 260,000) were dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (17).

After the homogeneous mixed solution (17) was applied on a glass plate, the solvent was removed to obtain an uncured liquid film-like shaped product composed of the homogeneous mixed solution. The uncured liquid film-shaped product was colorless and transparent at room temperature (25 ° C.) to 100 ° C. While maintaining the temperature at 100 ° C., the ultraviolet intensity was 17 mW using two ultraviolet cut filters (manufactured by Toshiba, UV-D36B).
/ Cm ² was irradiated to the liquid film-like shaped object and cured. Further, in order to promote the reaction of the unreacted monomer in the coating film, after irradiating the ultraviolet light at 100 ℃ above,
Ultraviolet rays having an intensity of 70 mW / cm ² were irradiated at room temperature for 90 seconds to obtain a cured coating film (film thickness = about 100 μm).

The cured coating film thus obtained was colorless and transparent (light transmittance = 90%) at room temperature, and was in a good state without cracks. When the TEM observation of the cross section of the coating film was performed,
A network-like phase-separated structure having a diameter of 40 to 60 nm could be observed. Also, the result of the solvent extraction test performed in the same manner as in Example 1 was the same as in Example 1, except that methylene chloride was used instead of THF. Further, the surface hardness of the cured coating film was 5H or more.

[Comparative Example 7] A cured coating film was obtained in the same manner as in Example 17, except that the irradiation temperature of the ultraviolet ray was lowered 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 (light transmittance = 90%), and was good without cracks. However, the surface hardness of the cured coating film was 4H, which was inferior to the cured coating film obtained in Example 17.

Reference Example 4 The procedure of Example 17 was repeated except that no thermoplastic resin was used, no solvent was used, and the irradiation temperature was room temperature (25 ° C.). In the same manner as in No. 17, the DPCA-
20 alone cured product (film thickness = about 100 μm) was obtained, but the cured coating film had countless cracks, and a good coating film was not obtained.

[Example 18] As the active energy ray crosslinkable polymerizable compound, "Kayarad DPCA-20" 8
g, "Irgacure 184" as a photopolymerization initiator.
As a thermoplastic resin, 16 g of a styrene-acrylonitrile copolymer (manufactured by Scientific Polymer Co., Ltd., copolymer of Mw = 165000, ratio of acrylonitrile in all monomers constituting the copolymer = 32)
%) Was dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (18).

In Example 17, the homogeneous mixed solution (1
A cured coating film was prepared in the same manner as in Example 17 except that the homogeneous mixed solution (18) was used in place of 7), and the irradiation temperature of the ultraviolet ray was reduced to 17 mW / cm ² at an irradiation temperature of 60 ° C. It was created.

The uncured liquid film-shaped product was cloudy at room temperature (25 ° C.), but was colorless and transparent at 60 ° C. or higher. The cured coating film after the ultraviolet irradiation was thin and milky white, but was in a good state without cracks. When the TEM observation of the cross section of the coating film was performed, the size of the diameter was 0.2 to 0.2.
A network-shaped phase-separated structure of 6 μm could be observed.
Also, the results of the solvent extraction test performed in the same manner as in Example 1 except that methylene chloride was used instead of THF were shown in Example 1.
Was similar to Further, the surface hardness of the cured coating film was 5H or more.

Example 19 In Example 18, "TONE" was used instead of the styrene-acrylonitrile copolymer.
A homogeneous mixed solution (19) was obtained in the same manner as in Example 18, except that 2 g of "P-789" (polycaprolactone manufactured by Union Carbide Co., Ltd.) was used.

In Example 17, the homogeneous mixed solution (1
A cured coating film was prepared in the same manner as in Example 17 except that a homogeneous mixed solution (19) was used in place of 7), and the irradiation temperature of the ultraviolet ray was lowered to 17 mW / cm ² and the irradiation temperature of the ultraviolet ray was set to 60 ° C. It was created.

The uncured liquid film-shaped product was cloudy at room temperature (25 ° C.), but was colorless and transparent at 60 ° C. or higher. The cured coating film after the ultraviolet irradiation was thin and milky white, but was in a good state without cracks. When the TEM observation of the cross section of the coating film was performed, the size of the diameter was 0.2 to 0.2.
A network-shaped phase-separated structure of 6 μm could be observed.
Also, the results of the solvent extraction test performed in the same manner as in Example 1 except that methylene chloride was used instead of THF were shown in Example 1.
Was similar to Further, the surface hardness of the cured coating film was 5H or more.

Example 20 Example 18 was repeated except that 2 g of "Nippol AR-71" (acrylic rubber manufactured by Zeon Corporation) was used instead of the styrene-acrylonitrile copolymer. Similarly, a homogeneous mixed solution (20) was obtained.

In Example 17, the homogeneous mixed solution (1
A cured coating film was prepared in the same manner as in Example 17 except that the homogeneous mixed solution (20) was used in place of 7), and the irradiation temperature of the ultraviolet ray was reduced to 17 mW / cm ² and the irradiation temperature of the ultraviolet ray was set to 60 ° C. It was created.

The uncured liquid film-like shaped product was colorless and transparent at room temperature (25 ° C.) to 60 ° C. The cured coating film after the ultraviolet irradiation was thin and milky white, but was in a good state without cracks. When the cross section of the coating film was observed by TEM, a network-like phase-separated structure having a diameter of 0.2 to 0.6 μm could be observed. Also, the result of the solvent extraction test performed in the same manner as in Example 1 was the same as in Example 1, except that methylene chloride was used instead of THF. Further, the surface hardness of the cured coating film was 5H or more.

[0189]

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) C08L 27/06 C08L 27/06 29/14 29/14 31/04 31/04 55/00 55/00 67 / 00 67/00 71/12 71/12 75/04 75/04 // C08F 299/04 C08F 299/04 F term (reference) 4J002 AB02X AC03X AC07X AC08X AC09X BB24X BC03X BC07X BC09X BD04X BE06X BF02X BG04X BH01X BQ00W CF03X CF04X CF05X CF08X CF19X CH09X CK02X GH02 GJ02 GQ05 4J011 QA03 QA31 QA34 QA38 QA40 QA42 QA43 QA46 QB14 QB16 RA01 RA07 RA08 RA09 RA10 SA01 SA06 SA07 SA15 SA21 SA31 SA36 SA51 SA64 4J009 CC08 CA08 CC08 CA08 CC08 CC08

Claims (9)

[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 beam crosslinkable polymerizable compound is a polyester (meth) acrylate having 2 to 6 (meth) acrylic groups in one molecule, and (2) the thermoplastic resin is a polyester polymer, a phenoxy resin, vinyl Acetal polymer, vinyl chloride polymer, vinyl acetate polymer, styrene polymer, uncrosslinked rubber, urethane polymer, and at least one thermoplastic resin selected from the group consisting of cellulose derivatives. Characteristic resin composite. 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. Polyester (meth) acrylate having 2 to 6 (meth) acryl groups in one molecule is hydroxybivalic acid ester neopentyl glycol di (meth) acrylate or caprolactone-modified dipentaerythritol hexa (meth) ) Is an acrylate, wherein the thermoplastic resin is a polyester polymer, a phenoxy resin,
The thermoplastic resin is at least one thermoplastic resin selected from the group consisting of a vinyl acetal polymer, a vinyl chloride polymer, a vinyl acetate polymer, a styrene polymer, an uncrosslinked rubber, and a urethane polymer. 4. A resin composite having a bicontinuous structure according to 3. 5. The polyester (meth) acrylate having 2 to 6 (meth) acryl groups in one molecule is caprolactone-modified hydroxybivalic acid ester neopentyl glycol di (meth) acrylate, and the thermoplastic resin is 1 selected from the group consisting of polyester polymers, phenoxy resins, vinyl acetal polymers, vinyl chloride polymers, vinyl acetate polymers, styrene polymers, uncrosslinked rubbers, urethane polymers, and cellulose derivatives
5. The resin composite having a bicontinuous structure according to claim 1, which is the above thermoplastic resin. 6. An active energy ray-curable polyester (meth) acrylate having 2 to 6 (meth) acryl groups in one molecule, and (2) a polyester polymer, a phenoxy resin, or a vinyl acetal. A homogeneous mixture comprising a polymer, a chlorine-containing polymer, a vinyl acetate polymer, a styrene polymer, an uncrosslinked rubber, a urethane polymer, and one or more thermoplastic resins selected from the group consisting of cellulose derivatives. The method for producing a resin composite according to any one of claims 1 to 5, wherein, after shaping, the active energy ray is irradiated to induce phase separation and fix the bicontinuous structure. . 7. An active energy ray-curable polyester (meth) acrylate, (2) a thermoplastic resin, and (3)
7. The method for producing a resin composite according to claim 6, wherein after shaping a uniform mixed solution comprising a solvent for dissolving these components, the solvent is dried and removed, and thereafter, an active energy ray is irradiated. 8. The method for producing a resin composite according to claim 6, wherein the homogeneous liquid mixture contains a photopolymerization initiator, and the active energy rays are ultraviolet rays. 9. An active energy ray irradiation temperature of 50 to 20.
The method for producing a resin composite according to claim 6, wherein the temperature is 0 ° C.