JP3344732B2 - Reactive hot melt adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hot-melt type adhesive composition, which is particularly excellent in initial adhesiveness and heat resistance, is capable of performing initial bonding by hot melt, and is capable of real bonding by urethane curing reaction over time. The present invention relates to a reactive hot melt adhesive composition.

[0002]

2. Description of the Related Art In the field of adhesive compositions, a hot-melt type and a reactive type have been mainly known. The composition for hot-melt adhesives can be obtained by applying the heat-melted composition with a hot-melt applicator, cooling and solidifying to obtain an instantaneous adhesive force. Well known as However, such a hot-melt type adhesive composition has a remarkably low adhesive strength at a high temperature, and generally has a limit in adhesive reliability under an environment of 80 ° C. or more. Examples of the hot melt type adhesive composition include JP-A-49-25033, JP-A-51-90342, JP-B-58-17514, JP-A-58-67772, JP-A-58-147473,
JP-A-59-68385, JP-A-57-158276
Technologies such as ethylene-vinyl acetate, polyolefin (typically low-density polyethylene and atactic polypropylene), and block polymer (SIS, SB).
S, SEBS type, etc.), butyl rubber type, polyester type, polyamide type and the like are known. In addition, the hot melt type adhesive composition is used for bookbinding,
At present, it is widely used in industries such as packaging, textiles, furniture, woodworking, light electricity, and transportation.However, due to its heat-resistant adhesive strength, the range of use for each application is limited, and non-structural adhesives are used. Industry recognition as an agent. Particularly in the field of product assembly, there is a demand for an adhesive composition having a high heat resistance in a form utilizing the initial adhesive strength of hot melt as it is. Can not be used for the current situation. On the other hand, the reactive adhesive composition can be expected to have high temperature rigidity and adhesive strength, and is used as a structural adhesive. However, reactive adhesive compositions such as epoxy, urethane, and acrylic, which are generally well known, have extremely poor initial adhesiveness, and it is essential to increase the adhesive force by a curing reaction. Time is long and problematic.

[0003] In view of the above, various reactive hot-melt adhesive compositions having both characteristics such as initial adhesiveness of a hot-melt type and characteristics of a heat-resistant adhesive strength of a reactive type have been studied. For example, Japanese Patent Publication No. 47-518,
JP-A-98445 and JP-A-51-30898 disclose a reactive hot-melt adhesive composition comprising a urethane prepolymer specified as an ethylene-vinyl acetate resin and a tackifying resin. Have been. Also,
JP-A-52-37936, JP-A-52-123436
Hot-melt adhesive composition described in JP-A-56-45954 is a resin specified as any one of a polyethylene-based resin, a polyester-based resin, an ethylene-vinyl acetate resin-based resin, and an ethylene-ethyl acrylate-based resin. Disclosed are urethane prepolymers and tackifier resins. The reactive hot melt adhesive composition described in JP-A-63-120785 discloses a technique comprising a styrene block copolymer-based thermoplastic resin component and a specified urethane polyol. In this case, the styrene-based block copolymer-based thermoplastic resin component provides initial adhesiveness, and the toughness effect of the styrene-based block copolymer and the unsaturated hydrocarbon-based polyol represented by polybutadiene polyol and polyisoprene polyol; It is a disclosure that a cured product of a urethane prepolymer comprising a mixture of butylene glycol exhibits heat resistance and elasticity. Such a reactive hot-melt adhesive composition is disclosed technology in which initial adhesive strength is exhibited by a thermoplastic resin as a base polymer, and high-temperature rigidity is exhibited by a urethanization reaction over time. In general, the initial adhesiveness and heat resistance of the composition are insufficient. The reactive hot-melt adhesive compositions described in JP-A-62-181375 and JP-A-64-14287 disclose a technique comprising a room-temperature solid or crystalline polyurethane prepolymer. It has drawbacks in its properties. As described above, there is no moisture-curable reactive hot-melt adhesive composition that sufficiently satisfies the needs of the market, and a reactive hot-melt adhesive composition having excellent initial adhesiveness and heat resistance quickly. Is strongly desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the conventional drawbacks of the reactive hot-melt type composition, and to reduce the initial adhesive strength which is a characteristic of hot melt at the time of hot-melt coating with a known applicator. After coating and pressing, the hot melt is moisture-cured without damage and can be used as a quasi-structural or structural adhesive. A new reactive hot-melt adhesive composition with excellent initial adhesion and heat resistance. In providing things.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a reactive hot-melt adhesive composition, which comprises a molecular terminal
Polystyrene having a polymerizable carbon-carbon double bond
Or the styrene-containing copolymer and the alkyl group have 1 to 1 carbon atoms.
A graft obtained by copolymerizing 12 or more alkyl acrylates and one or more monomers selected from the group consisting of alkyl methacrylates having 1 to 12 carbon atoms in the alkyl group. A reactive hot melt adhesive composition comprising a polymer (A), a polyol (B) and a polyisocyanate (C). Or the molecular end
Polystyrene having a polymerizable carbon-carbon double bond
Or a styrene-containing copolymer and an alkyl group having 1 carbon atom.
A graft obtained by copolymerizing one or two or more monomers selected from the group consisting of alkyl acrylates having from 12 to 12 carbon atoms and alkyl methacrylates having from 1 to 12 carbon atoms in the alkyl group; The present invention relates to a reactive hot melt adhesive composition containing a polymer (A), a polyol (B), a polyisocyanate (C) and a tackifier resin (D). Here, a polymerizable carbon-carbon is added to the molecular terminal.
Polystyrene or styrene-containing
The polymer has a methacryloyl group introduced at the end of polystyrene or a methacryloyl group introduced at the end of a copolymer of styrene and acrylonitrile,
The number average molecular weight is preferably from 3,000 to 50,000.

Furthermore, the graft polymer (A) is divided
Having a polymerizable carbon-carbon double bond at the terminal
A group of 5-70 parts by weight of a styrene or styrene-containing copolymer , an alkyl acrylate having 1 to 12 carbon atoms in an alkyl group and an alkyl methacrylate having 1 to 12 carbon atoms in an alkyl group; It is preferable that one or two or more monomers selected from the group consisting of 95 to 30 parts by weight are copolymerized and the number average molecular weight is 8,000 to 200,000. The equivalent ratio (NCO / OH) of the hydroxyl group of the polyol (B) of the present invention to the isocyanate group of the polyisocyanate (C) is 1.2 to 5.0. The polyol (B) of the present invention is a polyether polyol, a polyester polyol, a polycarbonate polyol, a polybutylene polyol, a polybutadiene polyol, a polyisoprene polyol, a hydrogenated polybutadiene polyol, a hydrogenated polyisoprene polyol, a polyacrylate polyol, a castor oil and a derivative thereof. ,
One or two selected from the group of tall oil and derivatives thereof
Consists of more than species. Polyisocyanate (C) of the present invention
Is one or more selected from the group consisting of (hydrogenated) tolylene diisocyanate, (hydrogenated) diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate. .

The present invention also relates to the present invention, wherein the total amount of the polyol (B) and the polyisocyanate (C) is 90 to 10 parts by weight based on 10 to 90 parts by weight of the graft polymer (A).
Parts by weight, or the tackifying resin (D) is 150 parts by weight or less based on 100 parts by weight of the total amount of the graft polymer (A), the polyol (B), and the polyisocyanate (C). Is good. Further, the tackifying resin (D) is rosin and a derivative thereof,
(Hydrogenated) It is preferable to use one or more selected from the group consisting of terpene phenol resins and ketone resins. In the present invention, dibutyltin dilaurate may be added and blended in an amount of 0.01 to 5% by weight as a reaction hardening accelerator, or a tertiary amine compound may be added as a reaction hardening accelerator in an amount of 0.01 to 5% by weight. % By weight, and more preferably, 1,3-dimethylimidazolidinone as a tertiary amine compound as a reaction hardening accelerator in an amount of 0.01 to 5% by weight. It is good to consist. The present invention also relates to zinc oxide powder , magnesium oxide
Powder , metal powder , silica powder , calcium carbonate powder , titanium oxide
One or more dry fillers selected from powders, talc powders , alumina powders , carbon black powders , and the like may be used in an amount of 30% by weight or less. Hereinafter, the configuration of the present invention will be described in detail.

In the present invention , a polymerizable carbon-carbon atom
Polystyrene or styrene-containing copolymers with heavy bonds
The body is generally obtained by introducing a methacryloyl group at the end of polystyrene or by introducing a methacryloyl group at the end of a copolymer of styrene and acrylonitrile, and is synthesized by a living anion termination method or a chain transfer polymerization method. In the living anion termination method, styrene is subjected to living anion polymerization, and the growing living anion is reacted with a terminator having a double bond to synthesize a macromer.In the chain transfer polymerization method, chain transfer such as thioglycolic acid is performed. A macromer having a polymerizable carbon-carbon double bond by performing radical polymerization in the presence of an agent, introducing a functional group such as a carboxyl group into the polymer terminal, and reacting the functional group with, for example, glycidyl methacrylate. Are synthesized. In addition, polymerizable carbon is added to the molecular terminal.
-Containing polystyrene or styrene with carbon double bonds
The number average molecular weight of the copolymer is preferably from 3,000 to 50,000. If the number average molecular weight is less than 3,000, the cohesive force of the graft polymer is insufficient, and the initial adhesiveness of the adhesive composition is insufficient. The number average molecular weight is 5
If it is 0000 or more, poor coatability will result due to insufficient compatibility with the polyol or too high a melt viscosity of the adhesive composition. Examples of the alkyl acrylate having 1 to 12 carbon atoms and the alkyl methacrylate having 1 to 12 carbon atoms in the present invention include methyl (meth) acrylate, ( Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate
Butyl, isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, (meth)
Heptyl acrylate, octyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, (meth)
Examples include pentyl acrylate and benzyl (meth) acrylate.

Further , the polymerizable carbon-carbon is added to the molecular terminal.
Polystyrene with double bond or styrene-containing copolymer
The alkyl group having 1 to 12 carbon atoms of the alkyl group and the alkyl group having 1 to 12 carbon atoms;
When synthesizing the graft polymer by copolymerizing 12 methacrylic acid alkyl esters, if necessary, a monomer having a functional group copolymerizable with the monomer may be used as a copolymer component. Examples of such a monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid, hydroxyethyl (meth) acrylate, (meth) acrylic acid Monomers having a hydroxyl group such as hydroxypropyl, monomers having a glycidyl group such as glycidyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide and Unsaturated carboxylic acid amides having an amide group such as diacetone (meth) acrylamide, vinylpyridine, Monomers having an amino group such as dimethylaminoethyl acrylate and diethylaminoethyl (meth) acrylate, and a phosphate group such as acid phosphooxyethyl (meth) acrylate and acid phosphooxypropyl (meth) acrylate And the like. Further, vinyl acetate, acrylonitrile, methacrylonitrile, and the like can be copolymerized within a range that does not impair the features of the present invention. The graft polymer (A)
Has a polymerizable carbon-carbon double bond at the molecular end.
A group of 5-70 parts by weight of a styrene or styrene-containing copolymer , an alkyl acrylate having 1 to 12 carbon atoms in an alkyl group and an alkyl methacrylate having 1 to 12 carbon atoms in an alkyl group one or it is preferably composed of two or more monomers from 95 to 30 parts by weight of copolymerized selected from carbon polymerizable at a molecular end - carbon
Polystyrene with double bond or styrene-containing copolymer
If the combined amount is less than 5 parts by weight and the (meth) acrylic acid alkyl ester exceeds 95 parts by weight, the cohesive force of the adhesive composition is insufficient, and the initial adhesiveness is insufficient. Also, at the molecular end
Polystyrene having a polymerizable carbon-carbon double bond or
Means that the styrene-containing copolymer exceeds 70 parts by weight,
When the amount of the alkyl acrylate is less than 30 parts by weight, the compatibility with the polyol and the polyisocyanate is insufficient, and the initial adhesiveness of the adhesive composition is insufficient. Further, the number average molecular weight of the graft polymer (A) is 80
When the number average molecular weight is less than 8000, the cohesive force of the graft polymer and the adhesive composition is insufficient, and the initial adhesiveness is insufficient. Further, if the number average molecular weight exceeds 200,000, lack of compatibility with polyol and polyisocyanate or the melt viscosity of the adhesive composition is too high,
Coatability is poor.

[0010] The production of the graft polymer usually employs solution polymerization carried out in a solvent, but without using a solvent,
It may be polymerized in a urethane prepolymer or a tackifying resin prepared by reacting the polyol or the polyol with a polyisocyanate. Examples of the polymerization initiator include α, α′-azodiisobutyronitrile, benzoyl peroxide, acetyl peroxide, t-butylperoxypivalate, t-butylhydroperoxide, cumenehydroperoxide, and t-hexylperoxypiperide. Baleto,
2,2′-azobis- (2,4-dimethylvaleronitrile), lauroyl peroxide, t-butylperoxyneohexanoate, di-t-butyl peroxide, azodicyclohexylcarbonitrile, α, α-azodiiso Dimethyl butyrate, succinic peroxide, dicumene peroxide, dichlorobenzoyl peroxide and the like can be used. As the solvent, ethyl acetate, butyl acetate, benzene, toluene, xylene, cyclohexane, methanol, methyl ethyl ketone and the like can be used. Further, the equivalent ratio (NCO / OH) of the hydroxyl group of the polyol (B) to the isocyanate group of the polyisocyanate (C) is preferably 1.2 to 5.0, and the equivalent ratio is less than 1.2. In this case, a remarkable thickening phenomenon occurs with a decrease in the equivalent ratio, heat stability is lacking, and heat resistance after moisture curing is insufficient. on the other hand,
If it exceeds 5.0, the presence of a large amount of free isocyanate components causes environmental pollution due to the significant generation of free isocyanate vapor during application work. There is a problem that a foaming phenomenon occurs more than necessary with moisture.

The polyol (B) of the present invention includes polyether polyol, polyester polyol, polycarbonate polyol, polybutylene polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, polyacrylate polyol, castor Oil and its derivatives, tall oil and its derivatives, and the like. The polyether polyol is a homopolymer polyoxy obtained by ring-opening polymerization of propylene oxide and / or ethylene oxide in the presence of one or more low molecular active hydrogen compounds having two or more active hydrogens. Propylene polyol, polyoxyethylene polyol or polyoxyethylene-propylene polyol of random or block copolymer, propylene oxide and / or ethylene oxide adduct of bisphenol A and / or bisphenol F, and further obtained by ring-opening polymerization of tetrahydrofuran Polyoxytetramethylene glycol, etc., in which 2-3
Has two hydroxy groups.

Examples of low molecular weight active hydrogen compounds include diols such as ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and neopentyl glycol, and glycerin. , Trimethylolpropane, triols such as 1,2,6-hexanetriol, and amines such as ammonia, methylamine, ethylamine, propylamine and butylamine. The polyester polyol is usually produced by a reaction between a polybasic acid and a polyhydric alcohol or ring-opening polymerization of a polyhydric alcohol with ε-caprolactone, β-methyl-δ-valerolactone, etc. . The polybasic acid components include terephthalic acid, isophthalic acid, phthalic anhydride, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, eicosane diacid, dimer acid, paraoxybenzoic acid, trimellitic anhydride, and maleic acid. Acids and the like. As the polyhydric alcohol, in addition to the above-mentioned diols and triols, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polytetramethylene glycol,
1,4-cyclohexanedimethanol, pentaerythritol, polybutadiene diol, hydrogenated polybutadiene diol, 3-methyl-1,5-pentanediol, propylene oxide and / or ethylene oxide adduct of bisphenol A and / or bisphenol F, nonanediol And methyloctanediol.

The polyisocyanate (C) of the present invention includes (hydrogenated) tolylene diisocyanate, (hydrogenated) diphenylmethane diisocyanate and its modified products, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate. Phenylene diisocyanate, (hydrogenated) xylylene diisocyanate, meta-xylylene diisocyanate, and the like. Polymethylene polyphenyl polyisocyanate is particularly preferably used. The total amount of the polyol (B) and the polyisocyanate (C) is preferably 90 to 10 parts by weight based on 10 to 90 parts by weight of the graft polymer (A). When the total amount of the polyisocyanate exceeds 90 parts by weight, the cohesive strength of the adhesive composition becomes insufficient and the initial adhesiveness is remarkably reduced. On the other hand, when the amount exceeds 90 parts by weight of the graft polymer and the total amount of the polyol and the polyisocyanate is less than 10 parts by weight, the melt viscosity of the adhesive composition is too high, resulting in poor coatability.

The tackifying resin (D) of the present invention includes:
Rosin and its derivatives hydrogenated rosin, polymerized rosin, hydrogenated polymerized rosin, (hydrogenated) rosin glycerin ester, (hydrogenated) rosin pentaerythritol ester, disproportionated rosin glycerin ester and disproportionated rosin pentaerythritol ester, , (Hydrogenated) terpene phenolic resin, ketone resin, petroleum resin (aliphatic, aromatic, copolymerized, alicyclic and hydrogenated petroleum resin), (hydrogenated) terpene resin, cumaro Examples include rosin and its derivatives, (hydrogenated) terpene phenol resins and ketone resins. The tackifying resin (D) is preferably 150 parts by weight or less based on 100 parts by weight of the total of the graft polymer (A), the polyol (B) and the polyisocyanate (C). ), The total amount of polyol (B) and polyisocyanate (C) is 100 parts by weight, and if the tackifying resin (D) exceeds 150 parts by weight, the heat resistance of the adhesive composition after moisture curing will be insufficient. The reactive hot-melt adhesive composition of the present invention is composed of each of the above-mentioned compositions, and the following reaction hardening accelerator is added and blended in the range of 0.01 to 5% by weight for the purpose of further improving the reactivity. Things are much better.

As a preferred reaction hardening accelerator of the present invention,
As a result of intensive studies, it has been found that dibutyltin dilaurate and tertiary amines can be used alone or in combination. In particular, dibutyltin dilaurate and a tertiary amine of 1.3-
It has been found that the use of dimethylimidazolidinone alone or 1.3-dimethylimidazolidinone alone is particularly preferable because the action and odor can be satisfied simultaneously. Furthermore, as a result of intensive studies, the reactive hot melt adhesive composition of the present invention has the effect of further improving the coloring and thermal stability of the cured product, and adjusting the thermal expansion and shrinkage rates to reduce residual stress at the bonding interface. It has been found that it is preferable to add and blend the following fillers within 30% by weight for the purpose of effect. That is, as the most suitable filler for the reactive hot melt composition of the present invention, zinc oxide powder , magnesium oxide powder , metal powder , silica powder (including colloidal silica powder ), calcium carbonate powder , titanium oxide powder , talc powder , One or more dry fillers selected from the group consisting of alumina powder and carbon black powder are preferred. Especially zinc oxide powder ,
It has been found that the use of calcium carbonate powder , titanium oxide powder , talc powder , carbon black powder or the like significantly improves the weather resistance and has high thermal stability of the system. If the filler is used in an amount exceeding 30% by weight, the system exhibits a high thixotropy in terms of viscosity, resulting in a decrease in workability. Further, it is not preferable because there is an adverse effect such that the abrasion of the hot melt applicator is remarkably promoted. Further, in the reactive hot melt adhesive composition of the present invention, a conventionally known antioxidant (antiaging agent) such as a phosphite or a hindered phenol, an ultraviolet absorber such as benzotriazole, and an organic thixotrope There may be no problem at all in properly using an interface modifier such as a silane or titanate coupling agent. In the reactive hot melt adhesive composition of the present invention,
Thermoplastic polymers, waxes, plasticizers and the like can be added and compounded within a range that does not impair the characteristics.

The thermoplastic polymer includes ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methyl acrylate copolymer resin, styrene-isoprene-styrene block copolymer resin, and styrene-butadiene-styrene block copolymer. Polymer resin, styrene-ethylene-butylene-styrene block copolymer resin, styrene-ethylene-propylene-styrene block copolymer resin, ethylene-propylene copolymer resin, butyl rubber, isoprene rubber, isobutylene rubber,
Acrylic rubber, urethane rubber, nitrile rubber, ethylene-butene copolymer resin, ethylene-propylene-diene copolymer resin, polyester, polyamide, polyethylene,
Polypropylene and the like. Examples of the wax include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polymerized wax, low molecular weight polyethylene wax, low molecular weight polypropylene wax, natural wax (bee wax, spermaceti wax, carnauba wax, wood wax, montan wax, Ozokerite), modified wax and the like. Examples of the plasticizer include liquid polyisobutene, liquid polybutene, liquid (hydrogenated) polyisoprene, liquid (hydrogenated) polybutadiene, paraffinic oil, naphthenic oil,
Representative examples include epoxy plasticizers, phosphates, phthalates, dibasic aliphatic esters, and glycol esters. As a method for preparing the reactive hot melt adhesive composition of the present invention, for example, the following method can be employed. One is to carry out solution polymerization in a solvent at a reaction temperature of 70 to 80 ° C. to prepare a graft polymer (A). A urethane prepolymer prepared by reacting the polyol (B) and the polyisocyanate (C) at 80 ° C. for 5 hours in advance is added to the graft polymer solution and blended. If necessary, the tackifier resin (D) is added and blended, and the solvent is removed to obtain the desired product.

In a solvent at a reaction temperature of 70 to 80 ° C.,
The solution is polymerized to prepare the graft polymer (A). next,
The polyol (B) and, if necessary, the tackifying resin (D) are added to the graft polymer solution and blended. After melting, polyisocyanate (C) is added and blended.
For 5 hours to remove the solvent to obtain the desired product. Polymerization is performed in the polyol (B) at a reaction temperature of 70 to 80 ° C. to prepare the graft polymer (A). Next, the polyisocyanate (C) is added and reacted at 80 ° C. for 5 hours to obtain the desired product. If necessary, the tackifying resin (D) can be blended before or after the addition of the polyisocyanate. In the polyol (B) and the tackifier resin (D), the graft polymer (A) is prepared by polymerization at a reaction temperature of 70 to 80 ° C. Next, the polyisocyanate (C) is added and reacted at 80 ° C. for 5 hours to obtain the desired product. In addition, the graft polymer (A) is polymerized in the tackifying resin (D) at a reaction temperature of 70 to 80 ° C. to prepare the graft polymer (A). The polyol (B) and the polyisocyanate (C) are reacted at 80 ° C. for 5 hours in advance, and a urethane prepolymer adjusted and added to the graft polymer solution is blended to obtain the desired product.

[0018]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the evaluation of the composition adjusted in each Example and the comparative example was performed as follows. In the examples, "%" and "part" mean "% by weight" and "part by weight", respectively. (Measurement sample adjustment conditions) A 1-inch wide steel plate (polyester service coat surface) with a thickness of 0.3 mm
The reactive hot-melt adhesive composition melted at 20 ° C. was applied to a thickness of 200 μm, immediately put on a silk cloth, and lightly pressed with a rubber roll. After leaving the composition at room temperature for 30 minutes, the initial adhesive strength at 20 ° C. (T-peel strength)
Was measured. Further, it was left for one week in a thermo-hygrostat at 20 ° C./RH 60% and taken out.
A sample for measuring the mold peel strength was used. (Adhesive force measurement conditions) Adhesive force was determined by using a universal tensile tester (manufactured by Intesco Corporation) at a peeling speed of 10 mm / min and a T-type peel strength at each measurement temperature. (Melt viscosity) The melt viscosity at 120 ° C. was measured with a B-type rotational viscometer. (Number average molecular weight of graft polymer) It was measured by gel permeation chromatography (GPC) manufactured by JASCO Corporation using a tetrahydrofuran solvent.

Example 1 70 parts of n-butyl acrylate in 50 parts of ethyl acetate as a solvent, and a polymerizable carbon-carbon double bond at a molecular terminal.
CHEMLINK 4500 as polystyrene or styrene-containing copolymer having (molecular weight 13000, SA
RTOMER) 30 parts, α, α- as a polymerization initiator
0.4 parts of azoisobutyronitrile was added and the reaction temperature was 7
Polymerization was carried out at 0 ° C. for 5 hours to prepare a graft polymer solution. The number average molecular weight of this graft polymer is about 2000
It was 0. 45 parts of PPG Diol 3000 (molecular weight: about 3000, manufactured by Mitsui Toatsu Chemicals), which is a polypropylene glycol as a polyether polyol, and 15 parts of MDI-PH (manufactured by Mitsui Toatsu Chemicals), which is diphenylmethane diisocyanate, are added to the above graft polymer solution in advance. Was mixed and reacted at a temperature of 80 ° C. for 5 hours, and added and blended with 60 parts of a urethane prepolymer, followed by removing ethyl acetate to obtain an adhesive composition. At this time, the equivalent ratio (NCO / OH equivalent ratio) between the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate was 4.0.
The adhesive strength and melt viscosity of the adhesive composition thus prepared were measured. Example 2 As a solvent, 50 parts of 2-ethylhexyl acrylate in 40 parts of toluene, and a polymerizable carbon-carbon double at a molecular terminal.
50 parts of Macromer AS-6 (molecular weight: 6000, manufactured by Toa Gosei Chemical Co., Ltd.) as a polystyrene or styrene-containing copolymer having a bond, and 0.2 parts of benzoyl peroxide as a polymerization initiator were added, and the reaction temperature was 80%. Polymerized at ℃ for 5 hours,
A graft polymer solution was prepared. The number average molecular weight of this graft polymer was about 53,000. In the above graft polymer solution, Clapol P-2010 (molecular weight: about 2,000, poly (3-
After adding and mixing 79 parts of methyl-1,5-pentanediol adipate (manufactured by Kuraray Co., Ltd.), 2,4-tolylene diisocyanate, TDI-100 (manufactured by Mitsui Toatsu Chemicals, Inc.)
21 parts were added, reacted at a temperature of 80 ° C. for 5 hours, and detoluened to obtain an adhesive composition. NCO at this time
The / OH equivalent ratio was 3.0. The adhesive strength and melt viscosity of the adhesive composition thus prepared were measured.

[0020] As Example 3 solvent, in 50 parts of butyl acetate, 2-ethylhexyl 30 parts of acrylic acid, 10 parts of methyl methacrylate, minutes
Having a polymerizable carbon-carbon double bond at the terminal
CHEMLIN as a copolymer containing styrene or styrene
60 parts of K4545B (molecular weight: 4500, manufactured by SARTOMER) and 0.05 part of t-butyl peroxypivalate as a polymerization initiator were added, and the mixture was polymerized at a reaction temperature of 80 ° C. for 5 hours to prepare a graft polymer solution. The number average molecular weight of this graft polymer was about 120,000. Crapol A-2010 (having a molecular weight of about 20
129 parts of poly (1,4-butadienediol adipate, manufactured by Kuraray Co., Ltd.) and 21 parts of hexamethylene diisocyanate, that is, an equivalent ratio (NCO / OH)
2.0 parts and mixed with 150 parts of urethane prepolymer prepared by reacting at a temperature of 80 ° C. for 5 hours.
An adhesive composition was obtained by adding 50 parts of YS Polystar 2100 (terpene phenol resin, manufactured by Yasuhara Chemical Co., Ltd.) as a tackifier resin and then removing the butyl acetate. The adhesive strength and melt viscosity of the adhesive composition thus prepared were measured. Example 4 As a solvent, in 40 parts of toluene, 80 parts of isobutyl acrylate, having a polymerizable carbon-carbon double bond at a molecular terminal.
20 parts of Macromer AS-6 (molecular weight: 6000, manufactured by Toa Gosei Chemical Co., Ltd.) as a polystyrene or styrene-containing copolymer and 0.1 part of t-hexylperoxypivalate as a polymerization initiator were added at a reaction temperature of 80 ° C. Polymerization was performed for 5 hours to prepare a graft polymer solution. The number average molecular weight of this graft polymer was about 110,000. To the above graft polymer solution, 150 parts of D-2000 (molecular weight: about 2,000, manufactured by Toa Gosei Chemical Co., Ltd.) as polycaprolactone polyol and 200 parts of Foral 105 (hydrogenated rosin pentaerythritol ester, manufactured by Rika Hercules) as a tackifier resin. Was added, and the mixture was detoluened. Thereafter, 50 parts of isophorone diisocyanate was added, and the mixture was reacted at a temperature of 80 ° C. for 5 hours to obtain an adhesive composition. NCO / OH at this time
The equivalent ratio was 3.0. The adhesive strength and melt viscosity of the adhesive composition thus prepared were measured.

[0021] As Example 5 solvent, in 40 parts of ethyl acetate, 2-ethylhexyl 55 parts of acrylic acid, 20 parts of methyl methacrylate, minutes
Having a polymerizable carbon-carbon double bond at the terminal
CHEMLIN as a copolymer containing styrene or styrene
25 parts of K4500 (molecular weight: 13000, manufactured by SARTOMER) and 0.15 parts of t-hexylperoxypivalate as a polymerization initiator were added, and the mixture was polymerized at a reaction temperature of 70 ° C. for 5 hours to prepare a graft polymer solution. The number average molecular weight of this graft polymer was about 80,000. To the above graft polymer solution, 20 parts of ketone resin K-90 (ketone resin, manufactured by Arakawa Chemical Industry Co., Ltd.) was added as a tackifying resin, and the mixture was de-ethylated.
36 parts of URIC H-62 (manufactured by Ito Oil Co., Ltd.) as a castor oil derivative and 64 parts of MDI-LK (manufactured by Mitsui Toatsu Chemicals) as a modified diphenylmethane diisocyanate were added in advance.
100 parts of a urethane prepolymer prepared by reacting at 00 ° C. for 4 hours was added to obtain the desired product. At this time, the equivalent ratio (NCO / OH) was 2.5. The adhesive strength and melt viscosity of the adhesive composition thus prepared were measured. Example 6 In a urethane prepolymer prepared by reacting 15 parts of epol (molecular weight 2500, manufactured by Idemitsu Petrochemical Co.) as a hydrogenated polyisoprene polyol with 5.4 parts of 1,5-naphthalenediisocyanate at 100 ° C. for 4 hours. Has 89 parts of n-butyl acrylate, 1 part of hydroxyethyl methacrylate, and has a polymerizable carbon-carbon double bond at a molecular terminal.
CH as a polystyrene or styrene containing copolymer
EMLINK 4545B (Molecular weight 4500, SART
OMER) 100 parts, 2,2'-
Azobis (2,4-dimethylvaleronitrile) 0.4
And polymerized at a reaction temperature of 70 ° C. for 5 hours, and then dibutyltin dilaurate 0.02 as a reaction hardening accelerator.
% To obtain an adhesive composition. The number average molecular weight of this graft polymer was about 24,000. At this time, the equivalent ratio (NCO / OH) was 4.0. The adhesive strength and melt viscosity of the adhesive composition thus prepared were measured.

Example 7 N-butyl acrylate 20 was added as a polyester polyol in 249 parts of Plaxel 220 (polycaprolactone diol, molecular weight 2000, manufactured by Daicel Chemical Industries, Ltd.).
Part, ethyl acrylate 20 parts, polymerizable carbon at the molecular end
-Containing polystyrene or styrene with carbon double bonds
AN-6 as chromatic copolymer (molecular weight 6000, Toagosei Co., Ltd.) 60 parts, were added 0.2 parts of lauroyl peroxide as a polymerization initiator, and polymerization for 5 hours at a reaction temperature of 70 ° C., polyol / graft polymer A mixture was obtained. To this mixture, 51 parts of MDI-CRUDE200 (manufactured by Mitsui Toatsu Chemicals, Inc.), which is a polymethylene polyphenyl polyisocyanate, was added and reacted at 80 ° C. for 5 hours. Thereafter, 1,3-dimethylimidazolidinone was used as a reaction hardening accelerator. 0.5% was added to obtain an adhesive composition. The number average molecular weight of this graft polymer was about 21,000. At this time, the equivalent ratio (NCO / OH) was 1.5. The adhesive strength and melt viscosity of the adhesive composition thus prepared were measured. Example 8 Superester A-100 as a tackifier resin
(Disproportionated rosin glycerin ester, manufactured by Arakawa Chemical Industry Co., Ltd.) In 50.0 parts, 59 parts of 2-ethylhexyl acrylate, 1.0 part of acrylic acid , polymerizable carbon at the molecular terminal
-Containing polystyrene or styrene with carbon double bonds
AS-6 as chromatic copolymer (molecular weight 6000, Toagosei Co., Ltd.) 40 parts, as a polymerization initiator were added 0.15 parts of t- butyl peroxy hexanoate, 5 hours polymerization at a reaction temperature of 70 ° C. Thus, a tackifying resin / graft polymer mixture was obtained. In this mixture, 207 parts of NISSO-PB G-1000 (molecular weight: 1350, manufactured by Nippon Soda Co., Ltd.) as a polybutadiene polyol, a 2,4-substituted product, and a 2,6-substituted product are present in a ratio of 80:20.
/ 20-Tolylene diisocyanate (manufactured by Mitsui Toatsu Chemicals Co., Ltd.) (93 parts) was added, and a urethane prepolymer (300 parts) prepared by reacting at 80 ° C. for 5 hours was added. Was added to obtain an adhesive composition. The number average molecular weight of this graft polymer was about 62,000. At this time, the equivalent ratio (NCO / O
H) was 3.5. The adhesive strength and melt viscosity of the adhesive composition thus prepared were measured.

[0023] Comparative Example 1 Example-1 of n- butyl 70 parts of acrylic acid, the molecular end
Polystyrene having a polymerizable carbon-carbon double bond or
Is CHEMLINK 450 as a styrene-containing copolymer
The adhesive composition was prepared in the same manner except that 30 parts of 0 (molecular weight: 13000, manufactured by SARTOMER) was changed to 100 parts of butyl acrylate. Comparative Example 2 In 10 parts of ethyl acetate as a solvent, 14 parts of n-butyl acrylate, 6 parts of methyl methacrylate, and 0.05 part of α, α-azoisobutyronitrile as a polymerization initiator were added. Polymerization was performed at 70 ° C. for 5 hours to prepare a graft polymer solution. The number average molecular weight of this graft polymer was about 120,000. In the above graft polymer solution, 225 parts of PPG Diol 3000 (molecular weight: about 3000, manufactured by Mitsui Toatsu Chemicals), which is polypropylene glycol as a polyether polyol, and 75 parts of MDI-PH (manufactured by Mitsui Toatsu Chemicals), which is diphenylmethane diisocyanate, are added in advance. Were mixed, and 300 parts of a urethane prepolymer adjusted by reacting at a temperature of 80 ° C. for 5 hours was added and blended, and the mixture was de-ethyl acetate to obtain an adhesive composition. At this time, the NCO / OH equivalent ratio was 4.0. The adhesive strength and melt viscosity of the adhesive composition thus prepared were measured. Comparative Example 3 The graft polymer of Example 1 was replaced with Evaflex 22.
No. 0 (ethylene-vinyl acetate copolymer, manufactured by DuPont-Mitsui Polychemicals), except that the adhesive composition was prepared in the same manner. Comparative Example 4 The graft polymer of Example-4 was replaced with Kraton G-16.
The adhesive composition was prepared in the same manner except that 57 (styrene-ethylene butylene-styrene block copolymer resin, manufactured by Shell Chemical Co., Ltd.) was used.

[0024]

The reactive hot-melt adhesive composition of the present invention has better initial adhesiveness and heat resistance after curing than conventional reactive hot-melt adhesives, and is suitable for use in building materials and automobiles. It can be used effectively in the field of product assembly.

[0025]

[Table 1] Table 1

[0026]

[Table 2] Table 1-continued

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-359983 (JP, A) JP-A-4-31482 (JP, A) JP-A-2-272013 (JP, A) JP-A-61- 115977 (JP, A) JP-A-3-207782 (JP, A) JP-A-3-305881 (JP, A) JP-A-58-34878 (JP, A) JP-A-64-14287 (JP, A) JP-A-64-54087 (JP, A) JP-A-64-54089 (JP, A) JP-A-63-260974 (JP, A) JP-A-59-75975 (JP, A) (58) (Int.Cl. ⁷ , DB name) C09J 175/04

Claims (19)

(57) [Claims] 1. A polymerizable carbon-carbon double bond at a molecular terminal.
Having a polystyrene or styrene-containing copolymer , an alkyl acrylate having 1 to 12 carbon atoms and a methacrylic acid alkyl ester having 1 to 12 carbon atoms in the alkyl group. One
A reactive hot melt adhesive composition comprising a graft polymer (A), a polyol (B), and a polyisocyanate (C) obtained by copolymerizing one or more kinds of monomers. 2. A polymerizable carbon-carbon double bond at a molecular terminal.
Having a polystyrene or styrene-containing copolymer , an alkyl acrylate having 1 to 12 carbon atoms and a methacrylic acid alkyl ester having 1 to 12 carbon atoms in the alkyl group. One
Reactive hot melt adhesive containing a graft polymer (A), a polyol (B), a polyisocyanate (C) and a tackifying resin (D) obtained by copolymerizing one or more kinds of monomers Composition. 3. A polymerizable carbon-carbon double bond at a molecular terminal.
3. The polystyrene or styrene-containing copolymer having a methacryloyl group introduced at a terminal of polystyrene or a methacryloyl group introduced at a terminal of a copolymer of styrene and acrylonitrile. Reactive hot melt adhesive composition. 4. A polymerizable carbon-carbon double bond at a molecular terminal.
The reactive hot melt adhesive composition according to any one of claims 1 to 3, wherein the polystyrene or styrene-containing copolymer has a number average molecular weight of 3,000 to 50,000. 5. A graft polymer (A) is a heavy in molecular end
Polystyrene having a compatible carbon-carbon double bond or
5 to 70 parts by weight of a styrene-containing copolymer, selected from the group of alkyl acrylates having 1 to 12 carbon atoms in the alkyl group and alkyl methacrylate esters having 1 to 12 carbon atoms in the alkyl group 3. The reactive hot-melt adhesive composition according to claim 1, wherein 95 to 30 parts by weight of the obtained one or more monomers are copolymerized. 6. The reactive hot melt adhesive composition according to claim 1, wherein the number average molecular weight of the graft polymer (A) is 8,000 to 200,000. 7. An equivalent ratio (N) of a hydroxyl group of the polyol (B) to an isocyanate group of the polyisocyanate (C).
The reactive hot melt adhesive composition according to claim 1 or 2, wherein (CO / OH) is from 1.2 to 5.0. 8. Polyol (B) is a polyether polyol, polyester polyol, polycarbonate polyol, polybutylene polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, polyacrylate polyol, castor oil and The reactive hot melt adhesive composition according to any one of claims 1, 2 and 7 , which is one or a mixture of two or more selected from the group consisting of derivatives thereof, tall oil and derivatives thereof. object. 9. The polyisocyanate (C) is a group consisting of (hydrogenated) tolylene diisocyanate, (hydrogenated) diphenylmethane diisocyanate and modified products thereof, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate and polymethylene polyphenyl polyisocyanate. one or a mixture of two or more claims 1 to 7 reactive hot-melt adhesive composition according to any one of selected from. 10. The reactive hot melt according to claim 1, wherein the total amount of the polyol (B) and the polyisocyanate (C) is 90 to 10 parts by weight based on 10 to 90 parts by weight of the graft polymer (A). Mold adhesive composition. 11. The reaction according to claim 2, wherein the tackifying resin (D) is at most 150 parts by weight based on 100 parts by weight of the total of the graft polymer (A), the polyol (B) and the polyisocyanate (C). Hot melt adhesive composition. 12. The tackifier resin (D) is one or a mixture of two or more selected from the group consisting of rosin and its derivatives, (hydrogenated) terpene phenol resins and ketone resins. The reactive hot-melt adhesive composition according to the above. 13. The total amount of the graft polymer (A), the polyol (B) and the polyisocyanate (C) is 100% by weight.
To part, as a reaction curing accelerator, dibutyltin dilaurate, formed by 0.01 to 5 wt% additive formulation according to claim
2. The reactive hot melt adhesive composition according to 1. 14. A graft polymer (A), a polyol
(B), polyisocyanate (C) and tackifying resin
With respect to 100 parts by weight of the total amount of (D), a reaction hardening accelerator is used.
And dibutyltin dilaurate in an amount of 0.01 to 5% by weight.
3. The reactive hot melt type according to claim 2, which is added and blended.
Adhesive composition. 15. A graft polymer (A), a polyol
Total weight of (B) and polyisocyanate (C) 100 weight
Tertiary amine compound as a reaction hardening accelerator
2. The anti-reflection film according to claim 1, wherein the anti-reflection film is added and added in an amount of 0.01 to 5% by weight.
Responsive hot melt adhesive composition. 16. A graft polymer (A), a polyol
(B), polyisocyanate (C) and tackifying resin
With respect to 100 parts by weight of the total amount of (D), a reaction hardening accelerator is used.
And adding a tertiary amine compound in an amount of 0.01 to 5% by weight.
3. The reactive hot melt adhesive composition according to claim 2, comprising:
object. 17. The tertiary amine compound is 1,3-dimethyl
15. was or is imidazolidinone of 16 wherein the anti
Responsive hot melt adhesive composition. 18. A graft polymer (A), a polyol
Total weight of (B) and polyisocyanate (C) 100 weight
Parts, zinc oxide powder, magnesium oxide powder, metal powder,
Silica powder, calcium carbonate powder, titanium oxide powder, talc
Powder, alumina powder, carbon black powder
Up to 30% by weight of one or more dry fillers
The reactive hot according to claim 1, which is used for:
Melt type adhesive composition. 19. A graft polymer (A), a polyol
(B), polyisocyanate (C) and tackifying resin
(D) 100 parts by weight of the total amount of zinc oxide powder and
Gnesium powder, metal powder, silica powder, calcium carbonate powder,
Titanium oxide powder, talc powder, alumina powder, carbon black
One or more kinds of dry filling selected from the group of black flour
The agent is used within 30% by weight.
3. The reactive hot melt adhesive composition according to item 2.