JP5394607B2 - Adhesive composition - Google Patents

Description

  The present invention relates to an adhesive composition, a method for applying the adhesive composition, and a composite material.

Conventionally, various foams, such as a polystyrene foam and a polyethylene foam, are utilized as a building material, a structural material, and a heat insulation material.
Thermosetting resins such as epoxy resins, unsaturated polyester resins, polyurethane resins, phenol resins, melamine resins, and silicon elastomers are used as various structural materials.
Furthermore, these thermosetting resins are often combined with foams for light weight, imparting heat insulation, and economical reasons (see, for example, Patent Documents 1 to 4).

Specifically, Patent Document 1 describes that “polyvinylidene chloride-based foamed foam particles having a particle size of 0.01 to 5 mm and an expansion ratio of 3 to 100 times and 10 to 99% by volume, and thermosetting resins 1 to 90”. Composite material consisting of volume% ”([Claim 1]),“ a polyvinylidene chloride unfoamed bead containing a foaming agent having a particle size of 0.005 to 2 mm and a thermosetting resin raw material. , Bead / thermosetting resin raw material = 100/1 to 1/30 by weight ratio, the reaction heat at the time of curing the thermosetting resin, and the reaction heat and external heating simultaneously with the curing 2. A method for producing a composite material according to claim 1, wherein foaming is performed ([Claim 2]).
Similarly, Patent Document 2 states that “a composite material mainly composed of the following (1), (2), and (3). (1) Polychlorination having a particle diameter of 0.01 to 5 mm and an expansion ratio of 3 to 100 times. 10 to 99% by volume of vinylidene-based foamed foam particles (2) 1 to 90% by volume of thermosetting resin (3) 1 to 200% by weight with respect to 100 parts by weight of the total amount of (1) and (2) ([Claim 1]), "reaction heat at the time of curing a raw material mainly comprising the following (1), (2), (3), and the reaction heat and the outside from The method for producing a composite material according to claim 1, wherein foaming is performed simultaneously with curing by heating.
(1) Polyvinylidene chloride unfoamed beads containing a foaming agent and having a particle size of 0.005 to 2 mm.
(2) Thermosetting resin raw material. However, (1) / (2) = 100/1 to 1/30 (weight ratio)
(3) A reinforcing material of 1 to 200 parts by weight with respect to 100 parts by weight of the total amount of (1) and (2). Is described ([Claim 2]).

  Further, Patent Document 3 states that “a foaming vinylidene chloride resin particle having a foamed agent uniformly contained in partially crosslinked vinylidene chloride resin particles and having a multi-foamed structure stabilized by a crosslinked structure at the time of foaming or its A heat-expandable sealing agent comprising pre-expanded particles ”([Claim 1]) and an example using a modified silicone resin ([Example 1]). ).

  On the other hand, Patent Document 4 states that “a method for manufacturing a heat-insulating building panel that forms a floor, a wall, etc. of a house, and covers this surface on one surface of a frame having a peripheral frame in which frame materials are joined in a rectangular shape. A panel base having a shallow dish-shaped recess having a face material as a bottom surface by the attachment of the material is transported with the recess facing upward, and the panel base that is transported during transport A preheating step of preheating at least the recess; an application step of applying a foaming resin for heat insulation in the preheated recess in an unfoamed state; and a foaming heat insulating layer by foaming the applied foamable resin The manufacturing method of the panel for heat insulation building characterized by performing the process process including the curing process which forms ".

However, the composite materials described in Patent Documents 1 and 2 have a problem of poor adhesion to the adherend, and the thermally expandable sealing agent described in Patent Document 3 is resistant to water and heat on the adherend. There was an inferior problem.
In addition, the production methods described in Patent Documents 1, 2, and 4 have a problem that a material having excellent heat insulation cannot be obtained.

JP-A-6-39936 JP-A-6-155606 Japanese Patent Laid-Open No. 7-197014 Japanese Patent Laid-Open No. 7-148452

  Accordingly, the present invention provides an adhesive composition capable of obtaining a composite material having excellent adhesion (adhesiveness) to an adherend and excellent heat insulation, a method for applying the adhesive composition, and a composite material The task is to do.

  As a result of intensive studies to solve the above problems, the present inventor has found that an adhesive composition containing unfoamed heat-foamable microcapsules in either one or both of the main agent and the curing agent is adhesive to the adherend. The present invention has been completed by finding that it is an adhesive composition capable of obtaining a composite material having excellent (adhesion properties) and excellent heat insulation properties.

That is, the present invention provides the following (1) to ( 4 ).
(1) a base material component containing a crosslinkable silyl group-containing organic polymer (A);
It comprises a curing agent component containing an adhesion promoter (B),
The base component and / or the curing agent component contains unfoamed thermally foamable microcapsules (C),
The content of the thermally foamable microcapsule (C) is 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the crosslinkable silyl group-containing organic polymer (A) and the adhesion-imparting agent (B). Oh it is,
The adhesion-imparting agent (B) is a silane coupling agent,
The adhesive composition whose content of the said silane coupling agent is 0.1-50 mass parts with respect to 100 mass parts of said crosslinkable silyl group containing organic polymers (A) .
(2 ) The adhesive composition according to the above (1 ), wherein the ratio (after heating / before heating) of the volume before heating and the volume after foaming by heating is more than 1 and 100 or less.
(3) A construction method of the above (1) or adhesive composition according to any one of (2),
An application step of applying the adhesive composition to an adherend;
A construction method comprising: a heating step of heating the adhesive composition applied in the application step.
( 4 ) A composite material obtained by the method for applying an adhesive composition according to ( 3 ) above, wherein a heat insulating material adhered to the adherend is formed on the adherend.

As shown below, according to the present invention, an adhesive composition capable of obtaining a composite material having excellent adhesion (adhesiveness) to an adherend and excellent heat insulation, and construction of the adhesive composition Methods as well as composite materials can be provided.
In addition, if the adhesive composition of the present invention is used, the volume of the adhesive and the heat insulating material can be reduced in the construction method (composite material production stage), and the construction process can be simplified and the construction time can be shortened. It is very useful because it can be planned.
Furthermore, when the adhesive composition of the present invention is used, no special mold is required when forming the heat insulating material on the adherend, and therefore the heat insulating material is formed even on the adherend having a complicated shape. It is very useful because it can.

The adhesive composition of the present invention comprises a base material component containing a crosslinkable silyl group-containing organic polymer (A) and a curing agent component containing an adhesion promoter (B),
It is an adhesive composition containing unfoamed thermally foamable microcapsules (C) in the base material component and / or the curing agent component.
Hereinafter, the crosslinkable silyl group-containing organic polymer (A), the adhesion-imparting agent (B), and the thermally foamable microcapsule (C) will be described in detail.

<Crosslinkable silyl group-containing organic polymer (A)>
The crosslinkable silyl group-containing organic polymer (A) is an organic polymer having at least one crosslinkable silyl group shown below at the terminal or side chain.
Here, the crosslinkable silyl group is, for example, using a catalyst or the like as necessary in the presence of moisture or a crosslinking agent such as a silicon-containing group or silanol group having a hydrolyzable group bonded to a silicon atom. As a representative group, for example, a group represented by the following general formula (1) can be mentioned.

In the formula, R ¹ and R ² are each independently represented by an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ³ ) ₃ SiO—. And when two or more R ¹ or R ² are present, they may be the same or different.
Here, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ^{3 s} may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2.
In the t groups represented by the following general formula (2), b may be different. t shows the integer of 0-19. However, it is assumed that a + t × b ≧ 1 is satisfied.

The hydrolyzable group represented by Y is not particularly limited as long as it is a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Of these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Alkoxy groups such as groups are particularly preferred.
Among the crosslinkable silyl groups, a crosslinkable silyl group represented by the following general formula (3) is preferable from the viewpoint of easy availability. In the following general formula (3), R ² , Y and a have the same meanings as R ² , Y and a described above.

Specific examples of R ¹ and R ² in the general formula (1) include, for example, alkyl groups such as methyl group and ethyl group; alicyclic hydrocarbon groups such as cyclohexyl group; aryl groups such as phenyl group; benzyl group And a triorganosiloxy group represented by (R ³ ) ₃ SiO— in which R ³ is a methyl group or a phenyl group. R ¹ , R ² and R ³ are particularly preferably methyl groups.

  Therefore, the crosslinkable silyl group-containing organic polymer (A) is particularly limited as long as it is an organic polymer having at least one crosslinkable silyl group represented by the general formula (1) at the terminal or side chain. Specifically, for example, silyl group-containing polyether, silyl group-containing polyester, silyl group-containing vinyl polymer, silyl group-containing polyester modified vinyl polymer, silyl group-containing diallyl phthalate polymer, silyl group-containing Diaryl phthalate polymers, silyl group-containing polyisobutylenes, silyl group-containing ethylene / α-olefin copolymers, mixtures thereof and silyl group-containing organics of these copolymers (block copolymers, graft copolymers) A polymer etc. are mentioned.

  Among these, when the crosslinkable silyl group-containing organic polymer (A) is a silyl group-containing polyether, as the main chain polyether, ethylene oxide, propylene oxide, butene oxide, tetrahydrofuran and the like are used as raw materials. Preferred examples include those produced using cationic polymerization and anionic polymerization methods.

  When the crosslinkable silyl group-containing organic polymer (A) is a silyl group-containing polyester, examples of the main chain polyester include carboxylic acids such as maleic acid, succinic acid, glutaric acid, adipic acid, and phthalic acid, Obtained by ring-opening polymerization of polyester polyols or lactones prepared by reacting anhydrides, esters or halides thereof with a stoichiometric excess of polyols such as ethylene glycol, propylene glycol, and glycerin. Preferred examples include lactone polyols and the like.

When the crosslinkable silyl group-containing organic polymer (A) is a silyl group-containing vinyl polymer, it is possible to use an acrylic monomer as a vinyl monomer as a main component, and the resulting crosslinkable silyl group-containing organic polymer (A) This is preferable because the weather resistance and physical properties (modulus) of the adhesive composition of the present invention containing the above are improved.
Specific examples of the vinyl monomer include vinyl monomers mainly composed of cyclohexyl acrylate and / or butyl acrylate described in JP-A No. 2002-97449. Further, the above publication describes that a silyl group-containing vinyl polymer can be obtained by copolymerizing the vinyl monomer and an alkoxysilyl group-containing monomer. Furthermore, as a polymerization method, high-temperature continuous polymerization described in JP-A-57-502171 and JP-A-59-6207 can be used in addition to normal radical polymerization.

  When the crosslinkable silyl group-containing organic polymer (A) is a silyl group-containing polyisobutylene or a silyl group-containing ethylene / α-olefin copolymer, the main chain is disclosed in JP-A-4-154816, respectively. And what was manufactured by the method described in Unexamined-Japanese-Patent No. 2001-31719 is used.

  Moreover, it is preferable that the number average molecular weights of a crosslinkable silyl group containing organic polymer (A) are 1000 or more, and it is more preferable that it is 6000-30000. When the number average molecular weight is within this range, the adhesive composition of the present invention containing the crosslinkable silyl group-containing organic polymer (A) is easy to handle because the viscosity before curing is low, and the strength, elongation after curing, It is preferable because the physical properties such as modulus are good.

In the present invention, among those described above, a polyether is essentially a polyether, a polyether oligomer having at least one methyldimethoxysilyl group as a terminal or a side chain in the molecule, or the polyether It is preferable to use a crosslinkable silyl group-containing organic polymer containing a mixture of an oligomer and an acrylic oligomer having a methyldimethoxysilyl group.
Further, from the viewpoint of increasing the hardness of the heat insulating material formed on the adherend using the adhesive composition of the present invention obtained, it is preferably an organic polymer having three crosslinkable silyl groups, Further, from the viewpoint of lowering the hardness of the heat insulating material, an organic polymer having two crosslinkable silyl groups is preferable.

  In the present invention, as the crosslinkable silyl group-containing organic polymer (A), commercially available products such as MS polymer manufactured by Kaneka Chemical Industry Co., Ltd., Silyl, Epion, Exastar manufactured by Asahi Glass Co., Ltd. can be used.

<Adhesion imparting agent (B)>
The adhesion imparting agent (B) is not particularly limited as long as it is a conventionally known adhesion imparting agent. Specific examples thereof include a silane coupling agent, a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, and xylene. Resin etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.
Among these, the silane coupling agent is preferable because the adhesiveness of the obtained adhesive composition of the present invention to the adherend is further improved.

The silane coupling agent is not particularly limited as long as it is a conventionally known silane coupling agent as an adhesion-imparting agent, and specific examples thereof include aminosilane, mercaptosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or These mixtures or reactants, or compounds obtained by reacting these with polyisocyanates, and the like can be mentioned.
Among these, aminosilane and mercaptosilane are preferable because the adhesiveness of the obtained adhesive composition of the present invention to the adherend is further improved.

  The aminosilane is not particularly limited as long as it is a compound having an amino group or imino group and a hydrolyzable silicon-containing group. Specific examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (amino Ethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- ( Aminoethyl -3-aminopropyl ethyldiethoxysilane and the like.

  Specific examples of the mercaptosilane include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-mercaptopropylethyl. Examples include diethoxysilane.

Specific examples of vinylsilane include vinyltrimethoxysilane, vinyltriethoxysilane, and tris- (2-methoxyethoxy) vinylsilane.
Specific examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4- Epoxycyclohexyl) ethylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
Specific examples of methacrylic silane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Can be mentioned.
Specific examples of the isocyanate silane include isocyanate propyl triethoxy silane and isocyanate propyl trimethoxy silane.
Specific examples of the ketimine silane include ketiminated propyltrimethoxysilane and ketiminated propyltriethoxysilane.

In the present invention, by containing such an adhesion-imparting agent (B), the heat-insulating material formed on the adherend by using the obtained adhesive composition of the present invention and the adherend are bonded. The property is good.
Moreover, it is necessary to use the adhesive used in the current construction method, that is, the construction method in which the adhesive is applied onto the adherend and the heat insulating material is pressure-bonded by containing such an adhesion-imparting agent (B). Therefore, it is possible to simplify the construction process and shorten the construction time. This is applied to the adhesive composition of the present invention containing unfoamed thermally foamable microcapsules (C) to be described later together with the crosslinkable silyl group-containing organic polymer (A) and the adhesion-imparting agent (B). This is because the adhesive composition itself becomes a heat insulating material adhered to the adherend by applying and heating on the body.

  Moreover, in this invention, when using a silane coupling agent as an adhesion | attachment imparting agent (B), the content is 100 mass parts of said crosslinkable silyl group containing organic polymers (A) contained in a base material component. On the other hand, it is preferable that it is 0.1-50 mass parts, and it is more preferable that it is 0.5-5 mass parts. When the content of the silane coupling agent is in this range, the adhesive between the heat insulating material formed on the adherend using the adhesive composition of the present invention obtained and the adherend is better. It becomes.

<Heat-foaming microcapsule (C)>
The thermally foamable microcapsule (C) is a microcapsule that foams by heating, and in the present invention, it is contained in one or both of the base material component and the curing agent component in an unfoamed state. .

  A conventionally well-known thing can be used for the said thermally foamable microcapsule (C), As the specific example, the thermally foamable microcapsule which consists of a low-boiling-point solvent and the thermoplastic polymer wall material which includes it is suitable. It is mentioned in.

Here, as the thermoplastic polymer used for the thermoplastic polymer wall material, for example, acrylonitrile, acrylamide, acrylic acid, acrylic ester, methacrylonitrile, methacrylamide, methacrylic acid, methacrylic ester, vinyl chloride, vinylidene chloride, A homopolymer or copolymer such as vinyl acetate can be used. Also, a small amount of a crosslinking agent such as divinylbenzene, (poly) ethylene glycol (di) methacrylate, triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMP), triacryl formal (TAF) is added to these. Can also be used. Furthermore, these can be selected as appropriate based on the type and use of the resin.
Among these, from the viewpoint of foaming at a lower temperature, a vinylidene chloride polymer is preferable.

  Next, as the low boiling point solvent to be included, a hydrocarbon type solvent having a boiling point of -20 to 200 ° C. is preferably used. Specific examples of such a solvent include petroleum fractionation components such as n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, and petroleum ether.

  Moreover, it is preferable that the said heat-foamable microcapsule (C) is about 2-100 micrometers normally, and, as for a particle size, it is more preferable that it is about 5-50 micrometers.

  Further, the thermally foamable microcapsule (C) can be produced by a conventionally known method. Specifically, for example, a method described in Japanese Patent Publication No. 42-26524 can be used.

In the present invention, by containing such a heat-foamable microcapsule (C), the heat insulating property of the composite material obtained using the obtained adhesive composition of the present invention is improved, and the volume thereof is also reduced. be able to. This is because the heat-insulating material formed on the substrate using the adhesive composition of the present invention is independently foamed because the adhesive composition of the present invention contains the thermally foamable microcapsules (C) in an unfoamed state. This is considered to be because the foamed portion existing inside the heat insulating material tends to be discontinuous and the thermal conductivity is lowered.
Further, by containing such a heat-foamable microcapsule (C), no special mold is required when forming a heat insulating material on an adherend using the adhesive composition of the present invention obtained. Therefore, a heat insulating material can be formed even on an adherend having a complicated shape.

  Moreover, in this invention, content of the said heat-foamable microcapsule (C) is 0.1 with respect to a total of 100 mass parts of a crosslinkable silyl group containing organic polymer (A) and an adhesion | attachment imparting agent (B). It is preferable that it is -10 mass parts, and it is more preferable that it is 1-5 mass parts. Adhesiveness with the to-be-adhered body of the adhesive composition of this invention becomes it that content of the said heat-foamable microcapsule (C) is this range.

  In the adhesive composition of the present invention, the ratio of the volume before heating to the volume after foaming by heating (after heating / before heating) is preferably more than 1 and 100 or less, and preferably 1 to 50. Is more preferable, and it is still more preferable that it is 1-10. When the volume ratio is within this range, the adhesiveness of the adhesive composition of the present invention to the adherend becomes better.

The adhesive composition of the present invention preferably further contains a metal catalyst such as a tin catalyst, a zinc catalyst, or a titanium catalyst.
Specific examples of the tin catalyst include tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; a reaction product of dibutyltin oxide and phthalate; dibutyltin diacetylacetate Naruto.
Specific examples of the zinc catalyst include zinc octylate.
Specific examples of the titanium catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate.
In the present invention, these catalysts may be used alone or in combination of two or more.

The adhesive composition of the present invention can further contain an epoxy resin from the viewpoint of adjusting the hardness of the heat insulating material formed on the adherend.
A conventionally well-known epoxy resin can be used as such an epoxy resin.
Specifically, for example, epoxy compounds having a bisphenyl group such as bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type, and polyalkylene Bifunctional glycidyl ether type epoxy resins such as glycol type, alkylene glycol type epoxy compounds, epoxy compounds having a naphthalene ring, and epoxy compounds having a fluorene group;
Polyfunctional glycidyl ether type epoxy resins such as phenol novolac type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type;
Glycidyl ester epoxy resins of synthetic fatty acids such as dimer acid;
N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyldiaminodiphenylsulfone (TGDDS), tetraglycidyl-m-xylylenediamine (TGMXDA) represented by the following formula (4), (5) represented by triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, N, N-diglycidylaniline, tetraglycidyl 1,3-bisaminomethylcyclohexane (TG1,3-BAC), tri Glycidylamine epoxy resin such as glycidyl isocyanurate (TGIC);

Following epoxy compound having a tricyclo [5,2,1,0 ^2,6] decane ring represented by (6), specifically, for example, cresol or phenols, such as dicyclopentadiene and cresol An epoxy compound which can be obtained by a known production method of reacting epichlorohydrin after polymerization;

（式中、ｍは、０〜１５の整数を示す。）

(In the formula, m represents an integer of 0 to 15.)

Cycloaliphatic epoxy resin; epoxy resin represented by Toraythiol Co., Ltd. Frep 10 epoxy resin main chain having sulfur atom; urethane modified epoxy resin having urethane bond; polybutadiene, liquid polyacrylonitrile-butadiene rubber or acrylonitrile butadiene rubber Examples thereof include a rubber-modified epoxy resin containing (NBR).
These may be used alone or in combination of two or more.

  Among these epoxy resins, the bisphenol A type is preferable because the adhesiveness of the obtained adhesive composition of the present invention to the adherend is further improved.

  The adhesive composition of the present invention can contain various additives as required in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of the additive include a filler, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, a dispersant, and a thixotropic agent.

  Examples of the filler include wax stone clay, kaolin clay, calcined clay; fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, oxidized Magnesium; calcium carbonate, magnesium carbonate, zinc carbonate; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid ester treated products, and fatty acid ester urethane compound treated products.

Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the thixotropic agent include hydrogenated castor oil, silica, and talc.
The above additives can be used in combination as appropriate.

In the present invention, the substrate component containing the crosslinkable silyl group-containing organic polymer (A) contains only the crosslinkable silyl group-containing organic polymer (A) and the thermally foamable microcapsule (C). In the case where the thermally foamable microcapsule (C) is not contained, it may be a component containing only the crosslinkable silyl group-containing organic polymer (A). In addition, various additives described above (including metal catalysts and epoxy resins; the same shall apply hereinafter) may be included.
Similarly, the curing agent component containing the adhesion-imparting agent (B) may be a component containing only the adhesion-imparting agent (B) and the heat-foamable microcapsule (C). When it does not contain microcapsules (C), it may be a component containing only the above-mentioned adhesion-imparting agent (B), but it may contain the various additives described above as necessary.

  The method for producing the resin composition of the present invention is not particularly limited. For example, the base component containing the crosslinkable silyl group-containing organic polymer (A), the adhesion-imparting agent (B), and the unfoamed material are used. Mix the heat-foamable microcapsule (C) and the curing agent component containing the above-mentioned various additives, mix thoroughly at room temperature using a roll, kneader, extruder, universal stirrer, etc., and disperse uniformly ( Kneading).

The construction method of the adhesive composition of the present invention is the construction method of the adhesive composition of the present invention described above,
An application step of applying the adhesive composition to an adherend;
And a heating process for heating the adhesive composition applied by the application process.
Below, a coating process and a heating process are explained in full detail.

<Application process>
The said application | coating process is a process of apply | coating the adhesive composition of this invention to the to-be-adhered body surface which forms a heat insulating material.
Here, the adherend is not particularly limited because it varies depending on the application and location where a heat insulating material is required, and examples thereof include acrylic resin, polyester resin, float glass, and anodized aluminum.
Specific examples of the method for applying the adhesive composition of the present invention to an adherend include spray coating, dip coating, bar coater coating, and spin coating.

<Heating process>
The heating step is a step of heating the adhesive composition of the present invention applied in the application step, wherein the unfoamed thermally foamable microcapsule (C) is foamed and the crosslinkable silyl group-containing organic material is used. This is a step of curing the polymer (A).

In the present invention, until the unfoamed thermally foamable microcapsule (C) is sufficiently foamed, the crosslinkable silyl group-containing organic polymer (for example, modified silicone) is not cured. It is preferable to heat at about 60 to 150 ° C. for several tens of minutes, and more preferably at about 90 to 140 ° C. for about several tens of minutes.
Examples of the heating method include electromagnetic wave heating using an electromagnetic wave (for example, a method for radiating heat to a radiation plate), a method using a heater (for example, an electric heater), and a method for blowing warm air. Among these, electromagnetic heating is preferable.

  By the method for applying the adhesive composition of the present invention, a composite material in which a heat insulating material bonded to the adherend is formed on the adherend is obtained.

  Thus, according to the construction method of the adhesive composition of the present invention, it is necessary to use the adhesive used in the current construction method, that is, the construction method in which the adhesive is applied onto the adherend and the heat insulating material is pressure-bonded. Therefore, it is possible to simplify the construction process and shorten the construction time. As described above, the adhesive composition of the present invention containing the thermally foamable microcapsule (C) together with the crosslinkable silyl group-containing organic polymer (A) and the adhesion-imparting agent (B) is coated. This is because the adhesive composition itself becomes a heat insulating material adhered to the adherend by applying and heating on the adherend.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this.

(Examples 1-3, Comparative Examples 1-6)
Each composition component shown in the following Table 1 was mixed so that it might become a mass part shown in the following Table 1, and the adhesive composition was prepared.
Next, each prepared adhesive composition was coated on float glass (50 mm × 50 mm × 5 mm thickness) as an adherend, and then heated and dried at 140 ° C. for 10 minutes to insulate the adherend. A composite material on which the material was formed was produced.
Also, under the same conditions, each prepared adhesive composition was subjected to an anodized aluminum plate (50 mm × 50 mm × 3 mm thickness), an acrylic resin plate (50 mm × 50 mm × 3 mm thickness), and a polyester plate (50 mm × 50 mm × 3 mm thickness). And a composite material having a heat insulating material formed on the adherend was produced.

  About each obtained composite material, adhesiveness was measured with the following method. The results are shown in Table 1.

<Adhesiveness>
The evaluation of the adhesion of the heat insulating material to each adherend is carried out by leaving each prepared composite material to stand for 3 days under conditions of 23 ° C. and 55% RH, and then performing a hand peeling test with a knife cut. The state was observed visually.
In Table 1, TCF indicates that the heat insulating material as the adhesive composition has undergone thin-layer cohesive failure, and AF indicates that the heat insulating material as the adhesive composition has undergone adhesive failure (interface failure).

Each adhesive composition prepared by the same method as described above is put into a metallic mold (150 mm × 100 mm × 15 mm thickness) that has been subjected to a release treatment, and is heated and dried at 120 ° C. for 10 minutes, and then removed from the mold. A test piece consisting only of a heat insulating material was produced.
About each obtained test piece, the heat conductivity and volume ratio were measured with the following method. The results are shown in Table 1.

<Thermal conductivity>
The thermal conductivity of the surface of each obtained test piece was measured using a thermal conductivity meter (manufactured by Kyoto Electronics Co., Ltd.).

<Volume ratio>
Ratio of the volume of each adhesive composition (150 mm × 100 mm × 15 mm = 225 cm ³ ) placed in the mold when preparing the test piece to the volume of the test piece (heat insulating material) (test piece / adhesive composition) Was calculated. The results are shown in Table 1.

Each composition component in Table 1 is as shown below.
Crosslinkable silyl group-containing organic polymer A1: Modified silicone (MSP S203, manufactured by Kaneka Chemical Co., Ltd.)
Crosslinkable silyl group-containing organic polymer A2: Modified silicone (MSP S303, Kaneka Chemical Co., Ltd.)
Adhesion imparting agent B1: N-phenyl-γ-aminopropyltrimethoxysilane (Y9669, manufactured by Nihon Unicar)
Unfoamed microcapsule C1: Unfoamed thermally foamable microcapsule (Matsumoto Microsphere F-2, manufactured by Matsumoto Yushi Co., Ltd., average particle size: 10 to 20 μm, wall material: vinyl chloride copolymer, solid content: 70 mass %that's all)
-Tin catalyst: Dibutyltin dilaurate (Nippon Chemical Industry Co., Ltd.)
・ Zinc catalyst: Zinc octylate (Nippon Chemical Industry Co., Ltd.)

From the results shown in Table 1, the composite material produced from the adhesive compositions prepared in Examples 1 to 3 does not contain an adhesion-imparting agent (B) or an unfoamed thermally foamable microcapsule (C). It was found that the adhesiveness was better than the composite material prepared from the adhesive composition prepared in -6.
Moreover, the test piece which consists only of the heat insulating material produced from the adhesive composition prepared in Examples 1-3 is a heat conductivity as low as the test piece produced from the adhesive composition prepared in Comparative Examples 1-6. Since the rate was shown, it was found that heat insulation was excellent.
Furthermore, the heat insulating material produced from the adhesive composition prepared in Examples 1 to 3 was found to be more than 1 and 100 or less.

Claims (4)

A base material component containing a crosslinkable silyl group-containing organic polymer (A);
It comprises a curing agent component containing an adhesion promoter (B),
The base component and / or the curing agent component contains unfoamed thermally foamable microcapsules (C),
The content of the thermally foamable microcapsule (C) is 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the crosslinkable silyl group-containing organic polymer (A) and the adhesion-imparting agent (B). Oh it is,
The adhesion-imparting agent (B) is a silane coupling agent,
The adhesive composition whose content of the said silane coupling agent is 0.1-50 mass parts with respect to 100 mass parts of said crosslinkable silyl group containing organic polymers (A) . The adhesive composition according to claim 1, wherein a ratio (after heating / before heating) of a volume before heating and a volume after foaming by heating is more than 1 and 100 or less. It is the construction method of the adhesive composition according to claim 1 or 2 ,
An application step of applying the adhesive composition to an adherend;
And a heating step of heating the adhesive composition applied in the application step. The composite material by which the heat insulating material adhere | attached on this to-be-adhered body was formed on the to-be-adhered body obtained by the construction method of the adhesive composition of Claim 3 .