JP4422575B2 - Non-aqueous dispersion composition and adhesive - Google Patents

Description

  The present invention relates to a non-aqueous dispersion composition and an adhesive using the same.

Conventionally, latex or non-aqueous dispersions are widely used as adhesives, pressure-sensitive adhesives, sealing materials, paints, and the like. Non-aqueous dispersions are used for special applications that are inappropriate when water is present, such as applications that dislike water, applications that require quick drying, and applications that cannot be heated to evaporate water.
However, it is very difficult to sufficiently volatilize the non-aqueous solvent that is the dispersion medium from the non-aqueous dispersion. If such a volatilization step exists, it is industrially disadvantageous. Further, there is a problem that the adhesiveness is lowered unless the non-aqueous solvent is sufficiently volatilized.

  The present invention provides a non-aqueous dispersion composition in which unnecessary solvent does not remain after curing, the water content is small, and excellent film elasticity and adhesion can be obtained.

The present invention is a non-aqueous dispersion composition in which (A) a modified natural rubber latex is solvent-substituted with (B) a reactive diluent, and the (A) modified natural rubber latex is a natural rubber latex 100. It is obtained by polymerizing a total of 5 to 50 parts by weight of vinyl monomers with respect to parts by weight (in terms of solid content), and the periphery of natural rubber latex particles is covered with vinyl polymer , and natural rubber latex particles The shape of the vinyl polymer coating the layer is a continuous layer, or the shape of the vinyl polymer layer is the aggregate of the vinyl polymer particles and the natural rubber latex particles are coated. The thickness of the vinyl polymer layer or the particle size of the vinyl polymer particles Is an average value of 0.02 to 0.08 μm, and the insoluble content of the dry film of the modified natural rubber latex in cyclohexane is 80% by weight or more. That relates to non-aqueous dispersion composition.
Here, the ratio of the above-mentioned (A) modified natural rubber latex and (B) reactive diluent is (A) 5-80 parts by weight of modified natural rubber latex (in terms of solid content), (B) reactive dilution. The agent is 95 to 20 parts by weight (provided that (A) modified natural rubber latex (in terms of solid content) + (B) reactive diluent = 100 parts by weight).
Further, the vinyl monomers constituting the vinyl-based polymer, (meth) acrylic acid ester, or preferably a (meth) acrylic acid ester and the (meth) vinyl monomers other than acrylic acid ester.
Furthermore, as the reactive diluent, unsaturated carboxylic acid composed of acrylic acid or methacrylic acid, or an ester thereof, alkyl (meth) acrylate, cycloalkyl (meth) acrylate, halogenated alkyl (meth) acrylate, alkoxyalkyl (meta ) Acrylate, hydroxyalkyl (meth) acrylate, aminoalkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, ethylene Alkylene glycol consisting of glycol or polyethylene glycol, mono or di (meth) acrylate of polyoxyalkylene glycol, trimethylol proppant (Meth) acrylates, (meth) acrylamide or its derivatives, styrene, vinyltoluene, divinylbenzene, it is a diluent selected from the group consisting of N- vinyl carbazole, and N- vinylpyrrolidone are preferable.
The water content of the non-aqueous dispersion composition of the present invention is preferably 5% by weight or less.
Next, the present invention relates to a UV curable adhesive or a thermosetting adhesive comprising the non-aqueous dispersion composition.

  The non-aqueous dispersion composition of the present invention is one in which (A) a modified natural rubber latex is dispersed in (B) a reactive diluent that is a substitution solvent, and when it is cured and used as an adhesive. After curing, no unnecessary solvent remains, and the moisture content is small, so that excellent film elasticity and adhesiveness can be obtained.

(A) Modified natural rubber latex used in the non-aqueous dispersion composition of the present invention is (B) a modified natural rubber latex composition having improved mixing stability with a reactive diluent, for example, Since the periphery of the natural rubber latex particles is covered with a vinyl polymer, (B) the mixing stability with the reactive diluent is imparted. In the presence of the natural rubber latex, It can be obtained by polymerizing monomers.
In the above composition, the natural rubber latex particles and the vinyl polymer are relatively firmly bonded, so that the solubility of the dry film in the solvent can be reduced. For example, the insoluble content in cyclohexane is 80% by weight. This can be done.

  The natural rubber latex used in the present invention refers to a naturally occurring emulsion of rubber, and is not particularly limited as long as it is usually referred to as “natural rubber latex”. For example, a high ammonia type, a low ammonia type, a deproteinization type and the like can be mentioned.

Examples of vinyl monomers to be polymerized in the presence of natural rubber latex include (meth) acrylate monomers, or vinyl monomers other than (meth) acrylate esters and (meth) acrylate monomers, such as aromatic vinyl. Monomer, vinyl cyanide monomer, ethylenically unsaturated acid monomer, ethylenically unsaturated alcohol and ester thereof, and ethylenically unsaturated silane. Of these, (meth) acrylic acid ester monomers are preferred.
These can be used alone or in combination of two or more.

  The (meth) acrylic acid ester monomer is an ester of acrylic acid and methacrylic acid with an aliphatic, alicyclic or aromatic unsubstituted alcohol, which is also used in conventional aqueous acrylic emulsions. The term “unsubstituted” as used herein means having no group other than a hydrocarbon group. Examples of (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. , Pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) Decyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, (meth ) Benzyl acrylate, cyclohexyl (meth) acrylate, and the like. Also, (meth) acrylic acid having a cycloalkyl group that may contain a substituent such as (meth) acrylic acid alkyl esters containing (epoxy group) such as glycidyl (meth) acrylate or cyclohexyl (meth) acrylic acid. Examples include cycloalkyl esters, alkyl (meth) acrylates having an alkyl group containing a hydroxyl group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. It is done. Of these, methyl (meth) acrylate is preferred.

  Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, p-methoxystyrene, p-aminostyrene, p- There are acetoxystyrene, sodium styrenesulfonate, etc., among which styrene is preferable.

  Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, vinylidene cyanide, α-methoxyacrylonitrile, and acrylonitrile is particularly preferable.

  Examples of the ethylenically unsaturated acid monomer include ethylenically unsaturated carboxylic acid and ethylenically unsaturated sulfonic acid. Examples of ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, etc., and examples of ethylenically unsaturated sulfonic acids include vinyl sulfonic acid, And isoprene sulfonic acid.

  Examples of the ethylenically unsaturated alcohols and esters thereof include allyl alcohol, methallyl alcohol, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, allyl acetate, methallyl caproate, allyl laurate, And allyl benzoate.

Examples of the ethylenically unsaturated silane include vinyltriethylsilane, methylvinyldichlorosilane, dimethylallylchlorosilane, and vinyltrichlorosilane.
The use amount of vinyl monomers other than the above (meth) acrylic acid esters is usually 80% by weight or less, preferably 60% by weight or less in the total vinyl monomers.

  The amount of the vinyl monomer to be polymerized is preferably 5 to 50 parts by weight with respect to 100 parts by weight (in terms of solid content) of natural rubber latex. More preferably, it is 10 to 40 parts by weight. If the amount is less than 5 parts by weight, the amount of the vinyl polymer obtained by polymerizing the vinyl monomer is not sufficient, the surface of the natural rubber latex particles cannot be sufficiently covered, and the mixing stability cannot be imparted. On the other hand, if it exceeds 50 parts by weight, the physical properties of the natural rubber change, which is not preferable for practical use.

The modified natural rubber latex (A) used in the present invention is characterized in that the natural rubber latex particles are covered with a vinyl polymer obtained from the vinyl monomer as described above.
(A) In the modified natural rubber latex, in addition to the vinyl polymer covering the periphery of the natural rubber latex particles, the vinyl polymer mixed without covering the periphery of the natural rubber latex particles, and further polymerizing There are vinyl monomers that are not. Usually, the total amount of unpolymerized vinyl monomers is 10% by weight or less, preferably 5% by weight or less of the total vinyl monomers, and (A) the modified natural rubber latex is combined with (B) a reactive diluent. After solvent replacement, the solvent can be removed by reduced pressure, heating, azeotropic distillation, or the like.

In the composition of the present invention described above, the natural rubber latex particles and the vinyl-based polymer are relatively firmly bonded, so that the solubility of the dry film in the solvent can be reduced. For example, a solvent such as cyclohexane The insoluble content in can be 80% by weight or more.
A natural rubber polymer is soluble in a solvent such as cyclohexane, but a polymer such as a (meth) acrylic acid ester polymer is difficult to dissolve in a solvent such as cyclohexane. Thus, coating the surface of natural rubber latex particles with such a vinyl polymer can impart insolubility to a solvent such as cyclohexane. As described above, the composition of the present invention in which the surface of natural rubber latex particles is coated with a vinyl polymer layer or fine particles has good mixing stability with a solvent. If the insoluble content in the solvent is lower than 80% by weight, the mixing stability with the solvent is poor, which is not preferable. Here, examples of the solvent include non-hydrophilic organic solvents such as cyclohexane, ethyl ether, n-octane, and butyl acetate.

  A method for measuring the insoluble matter in cyclohexane will be described below. First, the modified natural rubber latex composition is dried at 35 ° C. for 12 to 18 hours to obtain a dry film. The dried film whose water content was confirmed to be 1% or less was cut into a cube having a side of 1 to 2 mm and introduced into approximately 0.2 mg into cyclohexane (60 ml) under stirring. Sealed and allowed to stand at 23 ± 3 ° C. for 12 to 18 hours and further stirred for 1 hour. Filter with No. 2 filter paper and measure the solid content of the filtrate. The insoluble content is calculated from the solid content of the filtrate and the dry film weight introduced into cyclohexane.

The shape of the vinyl polymer covering the natural rubber latex particles is a continuous state (vinyl polymer layer) or a shape in which vinyl polymer particles are aggregated, and the thickness of the vinyl polymer layer covering the periphery of the natural rubber latex particles or vinyl The average value of the particle diameter of the polymer particles is 0.02 to 0.08 μm. When the thickness of the vinyl polymer layer or the particle size of the vinyl polymer particles is less than 0.02 μm, the effect of mixing stability by coating the natural rubber latex particles is small, and (B) a reactive diluent and The mixture becomes unstable during mixing, and the viscosity increases remarkably over time. On the other hand, if it exceeds 0.08 μm, the amount of monomer necessary for coating the majority of the natural rubber latex particles becomes excessive, resulting in a change in the physical properties of the natural rubber, which is not preferable in practice.

  Here, the measuring method of the average value of the thickness of the vinyl polymer layer or the particle size of the vinyl polymer particles is based on a transmission electron micrograph. Take 5 or more photos of the same product, measure the thickness of the vinyl polymer layer or the particle size of the vinyl polymer particles adhering to the natural rubber particles from each photo, and average 25 measured values in total. Then, the average value of the thickness of the vinyl polymer layer or the particle diameter of the vinyl polymer particles is set.

In the modified natural rubber latex (A) used in the present invention, the periphery of the natural rubber latex particles is covered with a vinyl polymer (layer or particle) obtained by polymerizing the vinyl monomer as described above. Such a shape is not obtained by simply mixing natural rubber latex with a synthetic resin emulsion or the like having the same particle size, but can be obtained by mixing natural rubber latex particles and a vinyl monomer and then polymerizing them. .
The polymerization method may be any method as long as the natural rubber latex particles are covered with a vinyl polymer.

  In addition, various additives can be mix | blended with (A) modified natural rubber latex used for this invention as needed. For example, antioxidants such as phenols, organic phosphites, and thioethers; light stabilizers; ultraviolet absorbers; lubricants such as amides, organometallic salts, and esters; bromine-containing organics, phosphoric acids, three Flame retardants such as antimony oxide, magnesium hydroxide, red phosphorus; organic pigments; inorganic pigments; organic fillers; inorganic fillers; inorganic and organic antibacterial agents such as metal ions; stabilizers; anti-aging agents; thickeners; Antiseptics; antifoaming agents; tackifying resins; dispersants: plasticizers and the like can be added.

The modified natural rubber latex used in the present invention has a solid content concentration of usually 45% by weight or more, preferably 50% by weight or more, more preferably 53% by weight or more, and a viscosity of usually 10 to 500 mPa · s. , Preferably 20 to 350 mPa · s.
If this concentration is less than 45% by weight, a long time is required for solvent replacement, which is not preferable.
(A) When the solid content concentration of the modified natural rubber latex is low, it is preferably used after being concentrated so as to be 45% by weight or more.

In the non-aqueous dispersion composition of the present invention, the reactive diluent (B) used for solvent substitution has a dilution effect similar to that of conventional solvents, and further has a reactive double bond in the molecule. This reactive double bond reacts by irradiating heat or UV wave, and can form a polymer film.
Such reactive diluents include, for example, acrylic acid, unsaturated carboxylic acids such as methacrylic acid, or esters thereof, alkyl (meth) acrylates, cycloalkyl (meth) acrylates, halogenated alkyl (meth) acrylates, Alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, aminoalkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) ) Mono- or di (meth) acrylates of alkylene glycols such as acrylates, ethylene glycol, polyethylene glycols and polyoxyalkylene glycols, and trimethylolpropane tri Meth) acrylate, (meth) acrylamide or its derivatives, or other, styrene, vinyltoluene, divinylbenzene, N- vinylcarbazole, etc. N- vinylpyrrolidone.
These can be used alone or in combination of two or more.

In addition to the above, reactive diluents include polyethylene glycol diacrylate, polypropylene glycol diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, 1,6-hexanediol diacrylate, 1,9- Nonanediol diacrylate, 2-ethyl, 2-butyl-propanediol diacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, EO modified phenol acrylate, EO modified cresol acrylate, EO modified nonylphenol acrylate, methoxytriethylene glycol acrylate, EO modified 2 Ethylhexyl acrylate, isobornyl acrylate, dipropylene glycol acrylate, trimethylol pro Pan triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, methoxypolyethylene glycol methacrylate, polypropylene glycol dimethacrylate, EO-modified bisphenol A dimethacrylate, and the like can be used.
Moreover, as a reactive diluent, the oligomer of said acrylic compound which has a double bond can also be used.

The non-aqueous dispersion composition of the present invention is obtained by solvent substitution of the above-mentioned (A) modified natural rubber latex with (B) a reactive diluent.
In the present invention, the solvent replacement may be performed by mixing the above-mentioned (A) modified natural rubber latex and (B) reactive diluent and removing moisture from this mixture.

  At the time of mixing, the ratio of (A) the modified natural rubber latex and (B) the reactive diluent is 25% of the reactive diluent with respect to 100 parts by weight (in terms of solid content) of (A) the modified natural rubber latex. To 1,900 parts by weight, preferably 30 to 600 parts by weight, more preferably 40 to 250 parts by weight. If the reactive diluent is less than 25 parts by weight, the dispersion state of the non-aqueous dispersion cannot be maintained. On the other hand, when it exceeds 1,900 parts by weight, it becomes difficult to obtain the effect of modifying the cured film by (A) modified natural rubber latex.

  Water may be removed by any method, and examples thereof include heating, azeotropic distillation, reduced pressure, replacement with other solvents, addition of a flocculant, and centrifugation, ultrafiltration, and fractional filtration. For these methods, an optimum one may be used depending on the reactive diluent (B) to be used. For example, EO-modified bisphenol A diacrylate can be dehydrated under reduced pressure, and the mixture is reduced to 50 at 760 mmHg under reduced pressure. What is necessary is just to heat to degreeC.

  The moisture is removed as described above, and the water content of the non-aqueous dispersion composition is preferably 5% by weight or less. If the water content exceeds 5% by weight, it becomes an inhibitory factor at the time of thermal curing or UV reaction, causing the (B) reactive diluent to remain in the film, and further, moisture remains in the film, which is not practically preferable. . The water content is preferably 2% by weight or less, more preferably 0.5% by weight or less. In the non-aqueous dispersion composition of the present invention, in order to reduce the water content to 5% by weight or less, heating, azeotropic distillation, reduced pressure, substitution with other solvents, addition of a flocculant, centrifugation, ultrafiltration, fractional filtration And the like.

  In the thus obtained non-aqueous dispersion composition of the present invention, the ratio of (A) modified natural rubber latex and (B) reactive diluent is (A) modified natural rubber latex (in terms of solid content). The same applies hereinafter) 5 to 80 parts by weight, (B) 95 to 20 parts by weight of reactive diluent, preferably (A) 15 to 75 parts by weight of modified natural rubber latex, (B) reactive diluent 85 ~ 25 parts by weight, more preferably (A) 30 to 70 parts by weight of modified natural rubber latex, 70 to 30 parts by weight of reactive diluent (provided that (A) modified natural rubber latex + (B) reactive diluent = 100 parts by weight). (A) If the modified natural rubber latex is less than 5 parts by weight, the effect of modifying the cured film with the modified natural rubber latex cannot be obtained. On the other hand, if it exceeds 80 parts by weight, the dispersion state of the non-aqueous dispersion cannot be maintained.

Moreover, the average particle diameter of the (A) modified natural rubber latex in the non-aqueous dispersion is usually 0.03 to 5 μm, preferably 0.05 to 4 μm, and more preferably 0.1 to 3 μm. Particles having a particle size of less than 0.03 μm cannot be obtained because the natural rubber latex particles used have a particle size of 0.03 μm or more. On the other hand, if it exceeds 5 μm, the modified natural rubber latex particles may be aggregated and coarsened, and in the liquid state, sedimentation may occur and it may be difficult to obtain a uniform film during actual use. .
Here, the measuring method of the average particle diameter of the modified natural rubber latex particles is based on dynamic light scattering measurement. The same product is measured three times or more, and the average value thereof is defined as the average particle diameter of the modified rubber latex particles.

  In the present invention, a thermal crosslinking initiator or a UV polymerization initiator is further added to the above non-aqueous dispersion composition in an amount of 1 to 10 with respect to 100 parts by weight of the (B) reactive diluent in the non-aqueous dispersion composition. Part by weight, preferably 2 to 8 parts by weight, more preferably 3 to 7 parts by weight may be added. When the amount of these initiators is less than 1 part by weight, the reaction of the film is incomplete, which causes unreacted (B) reactive diluent to remain in the film. On the other hand, if it exceeds 10 parts by weight, the remaining initiator may cause deterioration of the film.

  Here, examples of the thermal crosslinking initiator include organic polymerization initiators that may be used in the production of the modified natural rubber latex (A).

  Moreover, what is used normally can be used as a UV polymerization initiator. For example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, oligo [2-hydroxy 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 3-methylacetophenone, 2,2-dimethoxy-2-phenyl Acetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin ethyl ether , Benzoin propyl ether, Michler's ketone, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl Propan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- ON, 2,4,6-trimethylbenzoylphenylphosphinate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- ON, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpen Le phosphine oxide, methyl benzoyl formate, thioxanthone, diethyl thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and the like.

  As these commercial products, EsacureKK, KIP150, 75LT (manufactured by Lambberty), Irgacure 184, 261, 369, 379, 500, 651, 819, 907, 1700, 1800, 1850, 2959, CGI-403, Darocur 953, 1116, 1173, 1664, 2273, 4265 (above, manufactured by Ciba Specialty Chemicals), Lucyrin TPO, LR8728, LR8883 (above, manufactured by BASF), Evercryl P36 (produced by Daicel UCB), Vicure 55 (Akzo) KAYACURE CTX, DETX, BP-100, BMS, 2-EAQ (manufactured by Nippon Kayaku Co., Ltd.), and the like.

Moreover, various additives can be mix | blended with the non-aqueous dispersion composition of this invention as needed. For example, antioxidants such as phenols, organic phosphites, and thioethers; light stabilizers; ultraviolet absorbers; amides, organometallic salts, esters, and other lubricants;
Bromine-containing organic, phosphoric acid, antimony trioxide, magnesium hydroxide, red phosphorus and other flame retardants, organic pigments; inorganic pigments; organic fillers; inorganic fillers; metal ion-based inorganic and organic antibacterial agents; stable Anti-aging agent; Viscosity modifier; Leveling agent; Preservative; Antifoaming agent; Polymerization inhibitor; Tackifying resin; Dispersant; Plasticizer;
Such an additive may be added at the time of mixing (A) the modified natural rubber latex and (B) the reactive diluent, or may be added after moisture removal after mixing.

Furthermore, in the non-aqueous dispersion composition of the present invention, a non-reactive solvent can also be added for adjusting the solid content concentration of the composition and adjusting the texture of the cured product.
Non-reactive solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monobutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol monoethyl ether acetate, 2-methylpentane-2, Various solvents used for mixing with (A) modified rubber latex, such as 4-diol, may be mentioned.

  In the non-aqueous dispersion composition of the present invention, in a thermosetting composition system containing a thermal crosslinking initiator, it can be thermoset and used as an adhesive or a gap filler. What is necessary is just to carry out as conditions for thermosetting at 60-200 degreeC for 1 to 30 minutes. If it is less than 60 ° C., curing does not proceed sufficiently. More preferably, it is 2 to 20 minutes at 80 to 150 ° C.

Further, in the non-aqueous dispersion composition of the present invention, in a composition system containing a UV polymerization initiator, it can be UV-cured and used as an adhesive or a gap filler. As UV curing conditions, ultraviolet irradiation is preferably performed at an irradiation dose of 100 to 500 mJ / cm ² . When the irradiation amount is less than 100 mJ / cm ² , the film is not sufficiently cured, and unreacted (B) reactive diluent remains in the film. On the other hand, if it exceeds 500 mJ / cm ² , excessive reaction shrinkage is not preferable. A more preferable irradiation amount is 150 to 400 mJ / cm ² .

In addition, the non-aqueous dispersion composition of the present invention can be cured with an electron beam and used as an adhesive or a gap filler.
The non-aqueous dispersion composition of the present invention can be used not only as an adhesive as described above but also as a polymer modifier by utilizing the rubber elasticity of natural rubber.

Examples are described below, but the present invention is not limited to the examples and the following examples.
In the examples, parts and% are based on weight unless otherwise specified.
Moreover, the measured value in an Example was measured with the following method.

<Mixing stability>
50 g of the reactive diluent (B) in the table was added to 100 g (solid content 50 g) of the (A) modified natural rubber latex composition under stirring, and the state was observed and judged by a 5-point method (5 good) ← → 1 inferior).
5: Good mixing stability 4: A small amount of agglomerates can be formed, but mixing is possible 3: Although the agglomerates are dispersed in lumps, they can be mixed.
2: Aggregates are generated when the composition is added, and mixing is impossible.
1: Agglomerates are generated immediately in a small amount of the composition and cannot be mixed <Substitution stability>
(A) 50 g of the reactive diluent (B) in the table was added to 100 g of the modified natural rubber latex composition (solid content 50 g), and those that could be mixed were heated to 50 ° C. under reduced pressure of 750 mmHg. Dehydration was performed, and the state was observed and judged by the 5-point method (5 good ← → 1 bad).
5: Good solvent substitution 4: The viscosity of the sample increases during processing, but mixing is possible and solvent substitution is possible.
3: Stagnation occurs during the treatment, but gradually disappears and solvent replacement is possible 2: Solvent replacement (dehydration) is possible, but stagnation occurs during processing and remains until the end.
1: The whole sample or more than half solidifies during processing and cannot be mixed <moisture content>
It was measured by the Karl Fischer method.

<Film elasticity>
The composition was cured and formed into a film. The test length of 20 mm was stretched by applying a load up to 60 mm, and the length of the film remaining as strain after releasing the load was measured (measured value = length after test−test length 20 mm).
5: 0-20mm
4: 21-30mm
3: 31-40mm
2: 41-50 mm
1: Above 51mm or break

<Adhesiveness>
The compositions obtained by the operations of Examples and Comparative Examples were applied on a polished SUS plate with a thickness of 8 μm, and further covered with a transparent film. A UV wave was irradiated from above to obtain a test specimen. The film and adhesive of the test specimen were cut into a 25 mm width, and the 90 ° peel adhesive strength defined in JIS Z0237 (adhesive tape / adhesive sheet test method) was measured.
In the thermosetting composition, heating was performed instead of UV waves to obtain a test body, and then an adhesive strength test was performed.

Example 1
Modified MMA grafted natural rubber latex [graft copolymer obtained by graft polymerization of 20 parts of methyl methacrylate as a vinyl monomer for modification to 100 parts of MGNR20 (natural rubber latex (solid content conversion) made by Etec Co., Ltd.) ), Solid content concentration = 50%] 50 parts (in terms of solid content) and 50 parts of EO-modified bisphenol A diacrylate (Daiichi Kogyo Seiyaku New Frontier BPE-20) were mixed, dehydrated under reduced pressure, and UV added as an additive. 5 parts of the polymerization initiator was mixed with 50 parts of the reactive diluent (B). Dehydration under reduced pressure was performed by heating the mixture to 50 ° C. under a reduced pressure of 750 mmHg. The water content of the obtained non-aqueous dispersion composition was 0.5%.
About the obtained non-aqueous dispersion composition, as composition performance, mixing stability, substitution stability and moisture content were evaluated by the above evaluation method, and as practical performance, film elasticity and adhesion were evaluated by the above evaluation method. I examined the sex. The results are shown in Table 1.

Example 2 to Example 5
Using the modified natural rubber latex (A) shown in Table 1, a non-aqueous dispersion composition was prepared in the same manner as in Example 1, and the mixing stability, substitution stability, moisture content, film elasticity, and adhesiveness were examined. It was. The results are shown in Table 1.

Example 6
A non-aqueous dispersion composition was used in the same manner as in Example 1 except that (A) modified natural rubber latex shown in Table 1 was used and the UV polymerization initiator in Example 1 was changed to a thermal crosslinking initiator (4 parts). Were prepared, and mixed stability, substitution stability, moisture content, film elasticity, and adhesion were examined. The results are shown in Table 1.

Comparative Example 1 to Comparative Example 2
Using the modified natural rubber latex (A) shown in Table 1, a non-aqueous dispersion composition was prepared in the same manner as in Example 1, and the mixing stability, substitution stability, moisture content, film elasticity, and adhesiveness were examined. It was. The results are shown in Table 1.

Comparative Example 3
A non-aqueous dispersion composition was prepared in the same manner as in Example 1 except that (A) modified natural rubber latex shown in Table 1 was used and the UV polymerization initiator of Example 1 was used as a thermal crosslinking initiator. The mixing stability, substitution stability, moisture content, film elasticity, and adhesion were investigated. The results are shown in Table 1.

Example 7 to Example 10
Non-aqueous dispersion in the same manner as in Example 1 except that (A) modified natural rubber latex and (B) reactive diluent shown in Example 1 were used and the mixing ratio thereof was changed as shown in Table 2. A composition was prepared and examined for mixing stability, substitution stability, moisture content, film elasticity, and adhesiveness. The results are shown in Table 2.

Example 11 to Example 12
A non-aqueous dispersion composition was prepared in the same manner as in Example 1 except that the UV polymerization initiator of Example 8 and Example 9 in Table 2 was used as a thermal crosslinking initiator, and the mixing stability, substitution stability, The water content, film elasticity, and adhesion were examined. The results are shown in Table 2.

Comparative Example 4
(A) A modified natural rubber latex was not used, and a UV polymerization initiator was added to (B) a reactive diluent, and water content, film elasticity, and adhesion were examined. The results are shown in Table 2.

Comparative Example 5
Non-aqueous dispersion in the same manner as in Example 1 except that (A) modified natural rubber latex and (B) reactive diluent shown in Example 1 were used and the mixing ratio thereof was changed as shown in Table 2. A composition was prepared and examined for mixing stability, substitution stability, moisture content, film elasticity, and adhesiveness. The results are shown in Table 2.

The non-aqueous dispersion composition of the present invention has excellent film elasticity and adhesiveness, and is an adhesive, coating agent, gap filler, puncture repair agent, and other polymer modifiers for imparting rubber elasticity to hard polymers. It can use suitably as.

Claims (7)

(A) Non-aqueous dispersion composition in which modified natural rubber latex is solvent-substituted with (B) reactive diluent, and (A) modified natural rubber latex is 100 parts by weight of natural rubber latex (solid content Conversion), a vinyl monomer obtained by polymerizing a total of 5 to 50 parts by weight of vinyl monomers, and surrounding the natural rubber latex particles with a vinyl polymer, and covering the natural rubber latex particles A layer in which the polymer shape is a continuous state or a shape in which vinyl polymer particles are aggregated and coated with natural rubber latex particles, and the average value of the thickness of the vinyl polymer layer or the particle size of the vinyl polymer particles is 0. with a .02～0.08Myuemu, is insoluble content in the cyclohexane dry film of the modified natural rubber latex is 80 wt% or more, the non-aqueous de Spurgeon composition.   (A) Modified natural rubber latex (solid content conversion) 5 to 80 parts by weight, (B) Reactive diluent 95 to 20 parts by weight (However, (A) Modified natural rubber latex (solid content conversion) + ( The non-aqueous dispersion composition according to claim 1, wherein B) reactive diluent = 100 parts by weight). Vinyl monomers constituting the vinyl polymer was used (meth) acrylic acid ester or (meth) acrylic acid ester and the (meth) vinyl monomers other than acrylic acid ester (A) a modified natural rubber latex, The non-aqueous dispersion composition according to claim 1 or 2. (B) The reactive diluent is an unsaturated carboxylic acid comprising acrylic acid or methacrylic acid, or an ester thereof, alkyl (meth) acrylate, cycloalkyl (meth) acrylate, halogenated alkyl (meth) acrylate, alkoxyalkyl (meta ) Acrylate, hydroxyalkyl (meth) acrylate, aminoalkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, ethylene Glycol or polyethylene glycol alkylene glycol, polyoxyalkylene glycol mono or di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, (meth) acrylamide or its derivatives, styrene, vinyltoluene, divinylbenzene, N- vinylcarbazole according to any one of claims 1-3 which as well as at least one selected from the group consisting of N- vinyl pyrrolidone, Non-aqueous dispersion composition. The non-aqueous dispersion composition according to any one of claims 1 to 4 , wherein the water content is 5% by weight or less. A UV curable adhesive comprising the non-aqueous dispersion composition according to any one of claims 1 to 5 . A thermosetting adhesive comprising the nonaqueous dispersion composition according to any one of claims 1 to 5 .