WO2010147130A1 - 水性接着剤組成物 - Google Patents
水性接着剤組成物 Download PDFInfo
- Publication number
- WO2010147130A1 WO2010147130A1 PCT/JP2010/060166 JP2010060166W WO2010147130A1 WO 2010147130 A1 WO2010147130 A1 WO 2010147130A1 JP 2010060166 W JP2010060166 W JP 2010060166W WO 2010147130 A1 WO2010147130 A1 WO 2010147130A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adhesive composition
- curing agent
- aqueous adhesive
- core
- composition according
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
Definitions
- the present invention relates to an aqueous adhesive composition, and more particularly to a one-component thermosetting aqueous adhesive composition that can be used as an adhesive composition for automobile interior materials.
- automotive interior materials for example, ceilings, door trims, instrument panels, dashboard silencers, center consoles, pillars, ornaments, rear parcels, seats, etc.
- polyolefins such as polypropylene and polyethylene, polyolefin skins, and polyurethane foams. It is manufactured by adhering a decorative material such as a fabric with polyurethane foam with an adhesive using a pressure forming method or a vacuum forming method.
- polychloroprene adhesives that apply adhesives by spraying have been used for such bonding, but from the viewpoint of environmental safety, polychloroprene adhesives can be replaced with halogen-free adhesives. It is desired.
- An object of the present invention is to release a solvent gas at the time of coating or drying, and can be used as an adhesive composition for an automobile interior material.
- an adhesive composition for a precoat in a vacuum forming method for an automobile interior material made of polyolefin is excellent in storage stability as a composition before coating, storage stability after coating formation, adhesion to polyolefin, heat resistance, etc. There is.
- an aqueous adhesive composition comprising (A) an acid-modified polyolefin resin and (B) a core-shell type curing agent.
- the present invention includes the following preferred embodiments. [1] (A) an acid-modified polyolefin resin; (B) A water-based adhesive composition comprising a core-shell type curing agent. [2] The aqueous adhesive composition according to [1], wherein the core of the core-shell type curing agent (B) comprises a compound capable of crosslinking with the acid-modified olefin resin (A).
- the acrylic copolymer has a glass transition temperature of ⁇ 30 ° C. or higher.
- the aqueous adhesive composition of the present invention is a one-component thermosetting aqueous adhesive composition, has no environmental safety problems, storage stability as a composition before coating, and storage stability after coating formation. Particularly excellent in properties, adhesion to polyolefins, heat resistance, and the like. Therefore, the aqueous adhesive composition of the present invention is particularly suitable as an adhesive composition for automobile interior materials (for example, ceilings, door trims, instrument panels, dash silencers, center consoles, pillars, ornaments, rear parcels, seat sheets, etc.). It can be suitably used as an adhesive composition for pre-coating in a vacuum forming method for polyolefin automobile interior materials.
- automobile interior materials for example, ceilings, door trims, instrument panels, dash silencers, center consoles, pillars, ornaments, rear parcels, seat sheets, etc.
- the aqueous adhesive composition of the present invention comprises an acid-modified polyolefin resin (A) as a base polymer.
- the acid-modified polyolefin resin (A) in the present invention include polypropylene (PP) modified by introducing an unsaturated dibasic acid (for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.) or its anhydride.
- PB Propylene-butene copolymer
- PBE propylene-butene-ethylene copolymer
- SEBS styrene-ethylene / butene-styrene copolymer
- EVA ethylene-vinyl acetate copolymer
- EAA ethylene-acrylate copolymer
- the amount of acid modification of the acid-modified polyolefin resin (A) is not particularly limited. For example, it is 1.0 to 50% by weight, preferably 1.0 to 10% by weight, more preferably based on the weight of the olefin resin. Is 1.0 to 5.0% by weight. If the acid modification amount is less than 1.0% by weight, the emulsion stability may be impaired. On the other hand, if it exceeds 50% by weight, the adhesion to the polyolefin adherend may be significantly reduced. is there.
- the amount of acid modification referred to here is a value calculated from the blending ratio during polymerization.
- the content (solid content) of the acid-modified polyolefin resin (A) in the aqueous adhesive composition of the present invention is not particularly limited, but is preferably 5 to 70, for example, based on the weight of the entire adhesive composition. % By weight, more preferably 10 to 50% by weight. If the resin content is less than 5% by weight, the adhesion to the polyolefin adherend may be reduced. On the other hand, if the resin content exceeds 70% by weight, the adhesive may be bonded when the temperature of the adhesive at the time of bonding decreases. There is a risk of failure.
- the melting point of the acid-modified polyolefin resin (A) is not particularly limited, but is preferably 150 ° C. or less, more preferably 130 ° C. or less from the viewpoint of adhesiveness.
- the aqueous adhesive composition of the present invention comprises a core-shell type curing agent (B) in addition to the acid-modified polyolefin resin (A).
- the “core-shell type curing agent” in the present invention is an emulsion in which the composition is different in the center part of the emulsion particle, the core part, the outer part of the emulsion particle, and the shell part, and the core part contains the composition accompanying crosslinking. Means an agent.
- the core of the core-shell type curing agent (B) is not particularly limited.
- a compound capable of crosslinking with the acid-modified olefin resin (A) for example, an epoxy group-containing resin or a monomer thereof (for example, bisphenol A and epichlorohydrin) Reaction products or mixtures of bisphenol A and epichlorohydrin), amine compounds (eg, ethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, polyamides, dicyandiamide, tertiary amines, imidazoles), etc. Is mentioned.
- an epoxy group-containing resin or a monomer thereof is used.
- the shell of the core-shell type curing agent (B) is not particularly limited, and examples thereof include acrylic copolymers (for example, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate). Polymer or copolymer), polyurethane resin copolymer, and the like. Of these, acrylic copolymers are preferred.
- the acrylic copolymer those having a glass transition temperature of ⁇ 30 ° C. or higher, preferably ⁇ 15 ° C. or higher are preferable. If the glass transition temperature is less than ⁇ 30 ° C., the storage stability of the adhesive composition may be lowered.
- the upper limit of the glass transition temperature of the acrylic copolymer is not particularly limited, but is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, from the viewpoint of increasing the lower limit temperature for heating the adhesive in advance during bonding.
- the weight ratio between the core and the shell of the core-shell type curing agent (B) is not particularly limited, but is preferably 10:90 to 90:10, more preferably 35:65 to, from the viewpoint of the stability of the encapsulated core portion. 60:40.
- the core-shell type curing agent (B) can be produced, for example, by emulsion polymerization by dispersing the core part in a solvent and dropping the shell part.
- the core-shell type curing agent (B) can be obtained as a commercially available product such as Asahi Kasei Polytron R-1000.
- the content (solid content) of the core-shell type curing agent (B) in the aqueous adhesive composition of the present invention is not particularly limited, but is preferably from 0.5 to, for example, based on the weight of the entire adhesive composition. It is 20% by weight, more preferably 1 to 10% by weight.
- the content of the core-shell type curing agent is less than 0.5% by weight, the heat resistance of the target adhesive may be insufficient.
- Stability may be impaired.
- the aqueous adhesive composition of the present invention may comprise an amine curing agent (C) as necessary. It does not specifically limit as amine type hardening
- the polyamine compound which can be divided into the following two groups (I) and (II) is mentioned.
- Aromatic polyamines such as 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine; 1,12-dodecane Diamine, 1,10-decanediamine, 1,8-octanediamine, 1,14-tetradecan
- the amount used may be usually selected in the range of an equivalent amount of amino group to an excess amount with respect to the carboxyl group of the COOH-modified polymer. When the amount is less than the equivalent, crosslinking failure occurs, heat resistance is impaired, and when the amount is excessive, the curing agent is liberated and tends to cause adhesion failure.
- (II) It can be obtained by reacting a diamine containing two amino groups or imino groups in one molecule with a carbonyl compound (aldehyde or ketone). Hydrolyzable reaction product.
- the diamine include dimethylaminopropylamine, diethylaminopropylamine, monomethylaminopropylamine, methyliminobispropylamine, hexamethylenediamine, 1,10-diaminododecane, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, and di- ⁇ .
- Aliphatic diamines such as diamines; 1,8-p-menthane diamine, isophorone diamine, diaminocyclohexane, 4,4′-methylenebis (cyclohexylmethylamine), 1,3-bisaminomethylsilane Rhohexane, 3-aminomethyl-3,3,5-trimethylcyclohexylamine, N, N′-di-i-butyl-isophorone-diamine, N-aminoethyl-piperazine, 3- (3-aminopropyl) -3, Alicyclic diamines such as 2-dimethyl-piperazine; x
- R 1 and R 2 are the same or different and are independently H, lower alkyl (methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, etc.), phenyl or Naphthyl, or R 1 and R 2 together form a cyclic hydrocarbon (eg, cyclohexane, cyclopentane), except when R 1 and R 2 are both H or naphthyl] Specifically, aliphatic aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde; aromatic aldehydes such as benzaldehyde; cyclopentanone, trimethylcyclopentanone, cyclohexanone, trimethylcyclohexanone, etc.
- lower alkyl methyl, ethyl,
- the reaction of the diamine and the carbonyl compound may be carried out under ordinary conditions.
- a suitable reaction solvent toluene, xylene, benzene, etc.
- a water absorbing agent molecular sieve, anhydrous magnesium sulfate, etc.
- a stoichiometrically equivalent or excessive amount of a carbonyl compound may be used with respect to the diamine, and the dehydration (moisture distillation) may be performed at room temperature or under heating. In this way, a hydrolyzable reaction product is obtained.
- the reaction product when aldehyde is used as the carbonyl compound is “aldimine”
- the reaction product when ketone is used is “ketimine”.
- ketimine is more unstable than aldimine and easily hydrolyzed. That is, in the case of aldimine, the standing stability is excellent even when a relatively low molecular weight diamine is used, but in the case of ketimine, the stability is poor with the low molecular weight diamine. Low)) diamines (solids) are desired. Moreover, if the reaction medium is also used as a carbonyl compound, it is more desirable because it is always in an equilibrium state.
- the amine-based curing agent (C) used in the aqueous adhesive composition of the present invention preferably has a melting point of 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher.
- the melting point of the amine curing agent is less than 60 ° C., the stability after application of the adhesive composition may be deteriorated.
- the upper limit of the melting point of the amine-based curing agent is not particularly limited, but is preferably 250 ° C. or less, more preferably 200 ° C. or less, from the viewpoint of developing heat resistance of the adhesive.
- the amount of the amine curing agent used is not particularly limited.
- the amino group equivalent of the amine curing agent is, for example, 1 equivalent of the carboxyl group of the acid-modified polyolefin resin. 0.005 to 1 equivalent, preferably 0.01 to 0.5 equivalent. If the amino group is less than 0.005 equivalent, crosslinking will be poor, heat resistance will be impaired, and if it is excessive, storage stability and heat-resistant adhesion will be poor.
- the aqueous adhesive composition of the present invention can contain conventionally known additives in adhesive compositions such as a tackifier, a viscosity modifier, and an antifoaming agent, if necessary.
- the tackifier is not particularly limited, and includes various conventionally known petroleum resins, rosin resins, terpene resins, coumarone-indene resins, xylene resins, phenol resins, and modified products of these resins. These can be used alone or in combination of two or more.
- the content (solid content) of the tackifier in the aqueous adhesive composition of the present invention is not particularly limited. For example, it is preferably 1 to 25% by weight based on the weight of the entire adhesive composition, Preferably, it is 5 to 18% by weight. Even if the content of the tackifier is less than 1% by weight or exceeds 25% by weight, the adhesiveness may be lowered.
- the aqueous adhesive composition of the present invention can be produced by sequentially adding and mixing the above components according to a conventional method.
- the aqueous adhesive composition of the present invention is a one-component thermosetting adhesive composition, such as an automobile interior material (for example, ceiling, door trim, instrument panel, dash silencer, center console, pillar, ornament, rear parcel, It can be suitably used as an adhesive composition for pre-coating in a vacuum forming method for seat sheets and the like.
- an automobile interior material for example, ceiling, door trim, instrument panel, dash silencer, center console, pillar, ornament, rear parcel
- the aqueous adhesive composition of the present invention is used for the polyolefin skin material.
- Example 1 to 3 and Comparative Examples 1 to 3 Each component shown in the following Table 1 (parts by weight: in the case of a component containing a solvent (such as water)) was blended to prepare each adhesive composition. Each obtained adhesive composition was evaluated as follows. The results are shown in Tables 1 to 3.
- Each component in Table 1 is as follows.
- the adhesive compositions of Examples 1 to 3 have good performance in terms of storage stability of the adhesive as a precoat adhesive, stability after formation of the adhesive film, and heat-resistant creep resistance. You can see that In addition, it was confirmed that the peel strength was improved by adding (C) an amine curing agent in the hot peel test. On the other hand, the adhesive compositions of Comparative Examples 1 to 3 do not have sufficient heat-resistant creep resistance when (B) the core-shell type curing agent is not added, and (C) the excess amount is increased only with the amine-based curing agent. Thus, it was confirmed that when heat resistant creep resistance was to be ensured, the storage stability of the adhesive itself decreased and the adhesiveness after film formation decreased.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、水性接着剤組成物、詳細には、自動車内装材用の接着剤組成物として使用可能な、一液型熱硬化性の水性接着剤組成物に関する。
すなわち、本発明は、以下の好適な実施態様を含む。
〔1〕(A)酸変性ポリオレフィン系樹脂と、
(B)コアシェル型硬化剤と
を含んでなる、水性接着剤組成物。
〔2〕コアシェル型硬化剤(B)のコアは、酸変性オレフィン樹脂(A)と架橋可能な化合物を含んでなる、上記〔1〕に記載の水性接着剤組成物。
〔3〕酸変性オレフィン樹脂(A)と架橋可能な化合物は、エポキシ基含有樹脂またはそのモノマーを含んでなる、上記〔2〕に記載の水性接着剤組成物。
〔4〕コアシェル型硬化剤(B)のシェルはアクリルコポリマーを含んでなる、上記〔1〕~〔3〕のいずれかに記載の水性接着剤組成物。
〔5〕アクリルコポリマーのガラス転移温度は-30℃以上である、上記〔4〕に記載の水性接着剤組成物。
〔6〕コアシェル型硬化剤(B)におけるコアとシェルとの重量比は、10:90~90:10である、上記〔1〕~〔5〕のいずれかに記載の水性接着剤組成物。
〔7〕(C)アミン系硬化剤をさらに含む、上記〔1〕~〔6〕のいずれかに記載の水性接着剤組成物。
〔8〕アミン系硬化剤(C)の融点は60℃以上である、上記〔7〕に記載の水性接着剤組成物。
〔9〕自動車内装用である、上記〔1〕~〔8〕のいずれかに記載の水性接着剤組成物。
〔10〕プレコート用である、上記〔1〕~〔9〕のいずれかに記載の水性接着剤組成物。
したがって、本発明の水性接着剤組成物は、自動車内装材(例えば、天井、ドアトリム、インパネ、ダッシュサイレンサー、センターコンソール、ピラー、オーナメント、リアパーセル、座席シート等)用の接着剤組成物として、特にポリオレフィン製の自動車内装材の真空成形工法におけるプレコート用接着剤組成物として、好適に使用することができる。
本発明における酸変性ポリオレフィン系樹脂(A)としては、例えば、不飽和二塩基酸(例えばマレイン酸、フマル酸、シトラコン酸、メサコン酸等)若しくはその無水物を導入して変性したポリプロピレン(PP)、プロピレン-ブテンコポリマー(PB)、プロピレン-ブテン-エチレンコポリマー(PBE)、スチレン-エチレン/ブテン-スチレンコポリマー(SEBS)、エチレン-酢酸ビニルコポリマー(EVA)、エチレン-アクリレートコポリマー(EEA)等が挙げられる。これらはそれ自体公知であり、商業上入手可能である。
ここでいう酸変性量は、重合時の配合比率により算出される値である。
上記酸変性ポリオレフィン系樹脂(A)の融点は特に限定されないが、接着性の観点から、好ましくは150℃以下、より好ましくは130℃以下である。
本発明における「コアシェル型硬化剤」とは、エマルジョン粒子の中心部、コアの部分とエマルジョン粒子の外郭部、シェルの部分で組成が異なり、コア部に架橋に伴う組成を内包したエマルジョンである硬化剤を意味する。
また、上記コアシェル型硬化剤(B)は、例えば、旭化成製ポリトロンR-1000等の市販品として、入手することができる。
(I)融点60℃以上、好ましくは80~200℃の固形ポリアミン化合物、たとえば4,4’-ジアミノジフェニルメタン、2,4’-ジアミノジフェニルメタン、3,3’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、2,2’-ジアミノビフェニル、2,4’-ジアミノビフェニル、3,3’-ジアミノビフェニル、2,4-ジアミノフェノール、2,5-ジアミノフェノール、o-フェニレンジアミン、m-フェニレンジアミン、2,3-トリレンジアミン、2,4-トリレンジアミン、2,5-トリレンジアミン、2,6-トリレンジアミン、3,4-トリレンジアミン等の芳香族ポリアミン;1,12-ドデカンジアミン、1,10-デカンジアミン、1,8-オクタンジアミン、1,14-テトラデカンジアミン、1,16-ヘキサデカンジアミン等の脂肪族ポリアミン;ヒドラジド系ポリアミン、たとえばドデカンジオヒドラジド、式:
上記ジアミンとしては、たとえばジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン、モノメチルアミノプロピルアミン、メチルイミノビスプロピルアミン、ヘキサメチレンジアミン、1,10-ジアミノドデカン、エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ジエチレントリアミン、ジ-β-アミノエチルスルフィド、ジ-β-アミノエチルジスルフィド、ジ-β-アミノエチルエーテル、ジ-γ-アミノ-n-プロピルエーテル、トリグリコールジアミン、N,N-ジ-i-ブチル-トリメチル-ヘキサメチレンジアミンなどの脂肪族ジアミン;1,8-p-メンタンジアミン、イソホロンジアミン、ジアミノシクロヘキサン、4,4’-メチレンビス(シクロセキシルアミン)、1,3-ビスアミノメチルシクロヘキサン、3-アミノメチル-3,3,5-トリメチルシクロヘキシルアミン、N,N’-ジ-i-ブチル-イソホロン-ジアミン、N-アミノエチル-ピペラジン、3-(3-アミノプロピル)-3,2-ジメチル-ピペラジンなどの脂環族ジアミン;キシリレンジアミン、ジアミノジフェニルエーテル、フェニレンジアミン、トリアミノキシレン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルプロパン、4,4’-ジアミノジフェニルエーテルなどの芳香族もしくは芳香族脂肪族ジアミンが挙げられる。特に炭素数8以上の脂肪族ジアミンが望ましい。
で示され、具体的にはアセトアルデヒド、プロピオンアルデヒド、n-ブチルアルデヒド、イソブチルアルデヒド、ジエチルアセトアルデヒドなどの脂肪族アルデヒド;ベンズアルデヒドなどの芳香族アルデヒド;シクロペンタノン、トリメチルシクロペンタノン、シクロヘキサノン、トリメチルシクロヘキサノンなどの環状ケトン;アセトン、メチルエチルケトン、メチルプロピルケトン、メチルイソプロピルケトン、メチルイソブチルケトン、ジエチルケトン、ジプロピルケトン、ジイソプロピルケトン、ジブチルケトン、ジイソブチルケトンなどの脂肪族ケトンが挙げられる。
なお、ケチミンはアルジミンより不安定であり、加水分解され易い。すなわち、アルジミンの場合は、比較的低分子のジアミンを用いても放置安定性に優れるが、ケチミンの場合に低分子のジアミンでは安定性が悪くなるため、比較的高分子で安定な(活性度の低い)ジアミン(固形)の使用が望まれる。しかも、反応媒体がカルボニル化合物兼用であれば、常時平衡状態にあるので、更に望ましい。
また、本発明の水性接着剤組成物における粘着付与剤の含有量(固形分)は特に限定されないが、例えば、接着剤組成物全体の重量を基準にして、好ましくは1~25重量%、より好ましくは5~18重量%である。粘着付与剤の含有量が1重量%未満であっても、25重量%を超えても接着性を低下させる虞がある。
例えば、本発明の水性接着剤組成物を使用して自動車内装材のポリオレフィン製の基材とポリオレフィン製の表皮材を接着する場合、まず、本発明の水性接着剤組成物をポリオレフィン製表皮材の接着面にスプレー塗布、もしくはロールコーター、カンマコーターなどで塗布した後、溶媒である水を常温もしくは熱風などの加熱乾燥装置を用いて乾燥させ、表皮材に接着剤の皮膜を形成させる。このようにして予め塗布された表皮材を再び加熱し、速やかにポリオレフィン製基材と貼りあわせる事により使用される。貼り合わせの際は基材側に細孔を設け裏面から吸引することで、表皮材を貼り合わせる真空成形工法を用いることで効果的に接着させることができる。
下記表1に示す各成分(重量部:溶媒(水など)を含む成分の場合、溶媒も含めた値)を配合し、各接着剤組成物を製造した。得られた各接着剤組成物を、下記のように評価した。その結果を表1~3に示す。
(1)常態剥離(室温(20℃)および100℃熱間)
下記の条件にて接着剤組成物を塗布および乾燥して基材と表皮材とを貼り合せ、20℃、65%RH(相対湿度)にて24時間養生した後、室温下および100℃熱間で、剥離強度(N/25mm)を測定した。
(2)耐熱クリープ
下記の条件にて接着剤組成物を塗布および乾燥して基材と表皮材とを貼り合せ、20℃、65%RH(相対湿度)にて24時間養生した後、90℃にて24時間(荷重:50g、100g、150g)後の剥がれ長さ(mm)を測定した。
また、上記(1)および(2)の試験の際、次の評価も行った。
BAF:基材側からの界面破壊
CF:接着剤の凝集破壊
FMB:表皮材の材料破壊
(3)貯蔵安定性
接着剤組成物を40℃にて10日間放置後、外観の変化を評価し、さらに、上記(1)および(2)の評価を行った。
(4)塗膜形成後の貯蔵安定性
下記の条件にて接着剤組成物を塗布および乾燥して基材と表皮材とを貼り合せた後、70℃にて3日間放置後、上記(1)および(2)の評価を行った。
[塗工条件]
表皮材PPF(ポリプロピレンフォーム)×基材PP(ポリプロピレン)
接着剤組成物の塗布量:PPF側に0.3mmt
[貼り合わせ条件]
表皮乾燥:195℃×2分間
基材加熱:80℃×3分間
圧締:0.5kgf/cm2×30秒間
(A1)酸変性ポリプロピレン:東洋化成工業株式会社製NA-1001(mp100℃、変性率3%、固形分30%)
(A2)酸変性ポリプロピレン:東洋化成工業株式会社製NA-3003(mp125℃、変性率2.5%、固形分30%)
(A3)酸変性ポリプロピレン:東洋化成工業株式会社製NZ-1001(mp80℃、変性率2.2%、固形分30%)
(B)コアシェル型硬化剤:旭化成ケミカル株式会社製ポリトロンR-1000(シェル部のTg:-15℃、コア/シェル重量比:40/30、固形分:50%)
(C)アミン系硬化剤:ドデカンジオヒドラジド(mp190℃)
(D)粘着付与剤:東邦化学株式会社製QME-120(石油樹脂エマルジョン、固形分50%)
(E)アクリルエマルジョン:旭化成ケミカル株式会社製ポリトロンT-155
Claims (10)
- (A)酸変性ポリオレフィン系樹脂と、
(B)コアシェル型硬化剤と
を含んでなる、水性接着剤組成物。 - コアシェル型硬化剤(B)のコアは、酸変性オレフィン樹脂(A)と架橋可能な化合物を含んでなる、請求項1に記載の水性接着剤組成物。
- 酸変性オレフィン樹脂(A)と架橋可能な化合物は、エポキシ基含有樹脂またはそのモノマーを含んでなる、請求項2に記載の水性接着剤組成物。
- コアシェル型硬化剤(B)のシェルはアクリルコポリマーを含んでなる、請求項1~3のいずれかに記載の水性接着剤組成物。
- アクリルコポリマーのガラス転移温度は-30℃以上である、請求項4に記載の水性接着剤組成物。
- コアシェル型硬化剤(B)におけるコアとシェルとの重量比は、10:90~90:10である、請求項1~5のいずれかに記載の水性接着剤組成物。
- (C)アミン系硬化剤をさらに含む、請求項1~6のいずれかに記載の水性接着剤組成物。
- アミン系硬化剤(C)の融点は60℃以上である、請求項7に記載の水性接着剤組成物。
- 自動車内装用である、請求項1~8のいずれかに記載の水性接着剤組成物。
- プレコート用である、請求項1~9のいずれかに記載の水性接着剤組成物。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/377,928 US9359536B2 (en) | 2009-06-18 | 2010-06-16 | Aqueous adhesive agent composition |
CN2010800253842A CN102459488B (zh) | 2009-06-18 | 2010-06-16 | 水性粘接剂组合物 |
EP10789504.7A EP2444467B1 (en) | 2009-06-18 | 2010-06-16 | Aqueous adhesive agent composition |
CA2765452A CA2765452C (en) | 2009-06-18 | 2010-06-16 | Aqueous adhesive agent composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009145078A JP5615519B2 (ja) | 2009-06-18 | 2009-06-18 | 水性接着剤組成物 |
JP2009-145078 | 2009-06-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010147130A1 true WO2010147130A1 (ja) | 2010-12-23 |
Family
ID=43356446
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/060166 WO2010147130A1 (ja) | 2009-06-18 | 2010-06-16 | 水性接着剤組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9359536B2 (ja) |
EP (1) | EP2444467B1 (ja) |
JP (1) | JP5615519B2 (ja) |
CN (1) | CN102459488B (ja) |
CA (1) | CA2765452C (ja) |
WO (1) | WO2010147130A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020262350A1 (ja) * | 2019-06-28 | 2020-12-30 | 東亞合成株式会社 | 樹脂組成物、樹脂組成物層付き積層体、積層体、及び、電磁波シールドフィルム |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101467897B1 (ko) * | 2013-01-30 | 2014-12-02 | 후지모리 고교 가부시키가이샤 | 접착성 수지 조성물, 접착성 수지 성형체, 및 접착성 수지 적층체 |
GB201504291D0 (en) * | 2015-03-13 | 2015-04-29 | Dupont Teijin Films Us Ltd | PV cells |
CN106085295A (zh) * | 2016-07-21 | 2016-11-09 | 柳州市五源科技有限公司 | 环保无醛胶 |
EP3653672A4 (en) * | 2017-07-11 | 2021-03-31 | Sunstar Engineering Inc. | THERMALLY CROSS-LINKABLE COMPOSITION |
JP2020100797A (ja) | 2018-12-25 | 2020-07-02 | スリーエム イノベイティブ プロパティズ カンパニー | 水性接着剤組成物 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05311140A (ja) * | 1992-05-01 | 1993-11-22 | Three Bond Co Ltd | マイクロカプセル型接着剤組成物 |
JP2003272440A (ja) * | 2002-03-20 | 2003-09-26 | Shin Etsu Polymer Co Ltd | 異方導電接着剤及びヒートシールコネクタ |
JP2008260903A (ja) * | 2007-04-13 | 2008-10-30 | Unitika Ltd | 水性接着剤 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4552811A (en) * | 1983-07-26 | 1985-11-12 | Appleton Papers Inc. | Capsule manufacture |
US5030666A (en) * | 1986-07-14 | 1991-07-09 | Rohm And Haas Company | Multilobals |
JPH0641504A (ja) * | 1991-07-12 | 1994-02-15 | Saiden Kagaku Kk | アルカリ可溶型粘着剤組成物 |
EP0578498B1 (en) * | 1992-07-10 | 1997-04-16 | Nippon Shokubai Co., Ltd. | Acrylic polymer, its use and process for producing it |
JP3519298B2 (ja) | 1999-01-06 | 2004-04-12 | サンスター技研株式会社 | 一液型熱架橋性組成物 |
US7678847B2 (en) * | 2005-07-22 | 2010-03-16 | Appleton Papers Inc. | Encapsulated structural adhesive |
JP2007204669A (ja) * | 2006-02-03 | 2007-08-16 | Asahi Kasei Chemicals Corp | 特定小粒径粒度分布エポキシ樹脂用硬化剤およびエポキシ樹脂組成物 |
KR101463277B1 (ko) * | 2006-12-22 | 2014-11-26 | 바스프 에스이 | 카르보디이미드 기를 가지는 화합물을 포함하는 미세캡슐 |
-
2009
- 2009-06-18 JP JP2009145078A patent/JP5615519B2/ja active Active
-
2010
- 2010-06-16 CA CA2765452A patent/CA2765452C/en active Active
- 2010-06-16 EP EP10789504.7A patent/EP2444467B1/en active Active
- 2010-06-16 US US13/377,928 patent/US9359536B2/en active Active
- 2010-06-16 CN CN2010800253842A patent/CN102459488B/zh active Active
- 2010-06-16 WO PCT/JP2010/060166 patent/WO2010147130A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05311140A (ja) * | 1992-05-01 | 1993-11-22 | Three Bond Co Ltd | マイクロカプセル型接着剤組成物 |
JP2003272440A (ja) * | 2002-03-20 | 2003-09-26 | Shin Etsu Polymer Co Ltd | 異方導電接着剤及びヒートシールコネクタ |
JP2008260903A (ja) * | 2007-04-13 | 2008-10-30 | Unitika Ltd | 水性接着剤 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2444467A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020262350A1 (ja) * | 2019-06-28 | 2020-12-30 | 東亞合成株式会社 | 樹脂組成物、樹脂組成物層付き積層体、積層体、及び、電磁波シールドフィルム |
Also Published As
Publication number | Publication date |
---|---|
CN102459488A (zh) | 2012-05-16 |
EP2444467A4 (en) | 2012-11-14 |
US20120095130A1 (en) | 2012-04-19 |
CA2765452A1 (en) | 2010-12-23 |
CN102459488B (zh) | 2013-11-06 |
CA2765452C (en) | 2017-11-28 |
JP2011001444A (ja) | 2011-01-06 |
EP2444467B1 (en) | 2013-07-31 |
EP2444467A1 (en) | 2012-04-25 |
US9359536B2 (en) | 2016-06-07 |
JP5615519B2 (ja) | 2014-10-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5615519B2 (ja) | 水性接着剤組成物 | |
US20100035057A1 (en) | Primer composition and adhesive substrate | |
JP5363807B2 (ja) | 合成樹脂上に金属部材を固定するための熱活性化性フィルム | |
US11377576B2 (en) | Structural adhesive with improved corrosion resistance | |
CN110050052B (zh) | 耐受开放珠湿度暴露的环氧粘合剂 | |
US20130149531A1 (en) | Adhesive material | |
JP2002533511A (ja) | 耐衝撃性エポキシ樹脂系接着剤 | |
KR20050044798A (ko) | 저장 수명이 개선된 에폭시 조성물 및 이를 함유하는 제조품 | |
JP2008542483A (ja) | 合成樹脂上に金属部材を固定するためのニトリルゴムブレンドベースの接着シート | |
JP2009503176A (ja) | 合成樹脂上に金属部材を固定するためのニトリルゴム−ブレンドをベースとする接着剤シート | |
KR20160147786A (ko) | 프레-겔 오븐용 에폭시 수지 조성물 | |
JP2020512209A (ja) | 接着剤及び硬質基材に接着させる方法 | |
JP3406732B2 (ja) | 二液架橋型水性接着剤 | |
CN110325596B (zh) | 热交联性组合物 | |
JP3519298B2 (ja) | 一液型熱架橋性組成物 | |
JPH10287857A (ja) | 接着剤組成物、それを用いた接着方法ならびに化粧シート被覆材料の製造方法 | |
JPH0288684A (ja) | 接着方法及びそれに使用する液状接着剤 | |
JP3615470B2 (ja) | 制振接着ゴム組成物 | |
CN115427477B (zh) | 可固化组合物 | |
JPH03149256A (ja) | 架橋性組成物、その用途及び架橋方法 | |
JP5705071B2 (ja) | ヘミング用シーリング材組成物 | |
JP4155689B2 (ja) | 一液型架橋性組成物 | |
CN115427477A (zh) | 可固化组合物 | |
JPH07268307A (ja) | 水系熱接着型被覆組成物 | |
EP4328254A1 (en) | Applying structural adhesive |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080025384.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10789504 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2765452 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13377928 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010789504 Country of ref document: EP |