JP2005146130A - Reactive hot melt adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone reactive hot melt adhesive composition superior in thermal stability when heated and melted, capable of quickly hardening after adherence, and excellent in generation of heat resistance of a film. <P>SOLUTION: This reactive hot melt adhesive composition comprises a thermoplastic polymeric compound that comprises a hydrolytic silyl group such as an alkoxysilyl group, an organic group functionable as a hydrolytic catalyst for the hydrolytic silyl group, which is preferably a tertiary amino group or a carboxyl group, and a nitrogen atom containing bond selected from a urethane bond, a thiourethane bond, a urea bond, a substituted urea bond and a chemical bond derived from a Michael addition reaction in a molecule. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silicone-based reactive hot melt adhesive composition. More specifically, the present invention is excellent in thermal stability during heat-melting, has a fast curing reaction at room temperature, and has excellent heat resistance after coating. The present invention relates to a silicone-based reactive hot melt adhesive composition.

Hot melt adhesives can be applied at high speed due to the rapid onset of adhesive strength, and are solvent-free adhesives, so they have a low impact on the environment and have recently been used in various industrial fields. Has been.
However, conventional hot-melt adhesives can be applied by heating and melting, and since this takes a bonding mechanism that develops adhesive strength when cooled and solidified, bonding occurs when the adhesive is placed under high temperature conditions after bonding. There have been problems such as a decrease in adhesive strength accompanying the softening of the agent layer and peeling of the adhesive.
Therefore, in order to overcome these problems, there are various reactive hot melt adhesives that are thermoplastic during coating and bonding of the adhesive, but after coating and bonding, the heat resistance of the film is improved by chemical reaction. Has been developed.
Examples of such an adhesive include (1) a urethane-based reactive hot melt adhesive using a moisture curing reaction of an isocyanate group, and (2) a photocurable reactive hot melt that is reactively cured by irradiation with energy rays such as ultraviolet rays. Examples thereof include an adhesive, and (3) a silicone-based reactive hot melt adhesive utilizing a hydrolyzable silyl group hydrolytic crosslinking reaction.

Among these, the urethane-based reactive hot melt adhesive (1) is the most widely used reactive hot melt adhesive at present, such as Japanese Patent Publication No. 51-30898 and Japanese Patent Application Laid-Open No. 4-227714. In terms of practical use, for example, a honeycomb sandwich panel (Japanese Patent Publication No. 6-22756), a flexible packaging laminate (Japanese Patent No. 2733180), and an automobile ( JP-A-2001-11419) and fiber (Japanese Patent Publication No. 525917) are applied to various industrial fields.
However, although it is a urethane-based reactive hot melt adhesive having many advantages as described above, it is inevitably released in the product because it uses the reaction of isocyanate groups and moisture in the air for the curing reaction. Isocyanate monomers are included. For this reason, especially when used in a heated state, these free isocyanate monomers may be diffused and the working environment may be significantly deteriorated.

  In addition, the photo-curable reactive hot melt adhesive (2) is chemically reacted by irradiation with energy rays such as ultraviolet rays as disclosed in JP-A No. 2000-212540 and JP-A No. 7-3234. To cure the film. This type of reactive hot-melt adhesive can be post-irradiated with energy rays after bonding if the adherend is transparent to energy rays. Energy beam irradiation must be performed immediately before alignment. For this reason, there is a high possibility that the work process, apparatus / equipment, and even the adherend to be used are limited.

On the other hand, the silicone-based reactive hot melt adhesive (3) has a hydrolyzable silyl group by utilizing moisture in the air, as seen in JP 2000-34459 A and JP 2001-288366 A. The film is cured by hydrolysis crosslinking reaction.
This type of reactive hot melt adhesive does not contain a free isocyanate monomer like the urethane-based reactive hot melt adhesive of (1), so the working environment is good and the environment is low in load. . In addition, there is no need for equipment and facilities such as energy ray irradiation such as the photo-curable reactive hot melt adhesive of (2), and the reactive hot melt adhesive has advantages over the above adhesives. Many.

Here, in the conventional silicone-based reactive hot melt adhesive, as a catalyst for hydrolyzing the hydrolyzable silyl group, an organic metal compound such as dibutyltin dilaurate, a basic organic group having a tertiary amino group, etc. So-called transesterification catalysts such as compounds, acidic organic compounds having a carboxyl group and the like have been essential.
However, this transesterification catalyst promotes hydrolysis cross-linking reaction of hydrolyzable silyl groups, and at the same time, thermoplastic high molecular weight compounds such as polyester and acrylic resin commonly used as components of hot melt adhesives, tackifiers, adhesive properties It also has a hydrolytic action on the ester bond of the imparting agent and the like.

Therefore, when a large amount of these transesterification catalysts is added in order to promote the hydrolytic crosslinking reaction of the hydrolyzable silyl group after bonding, the above ester bond hydrolysis is performed in the heated and melted state before the adhesive coating. Decomposition tends to occur, and this may cause a decrease in the melt viscosity of the adhesive and a decrease in the final adhesive strength after the crosslinking reaction. In addition, since these catalysts have a relatively low molecular weight, they are likely to volatilize and dissipate in the heated and melted state, which may cause a deterioration of the working environment.
In addition, in order to suppress hydrolysis of the ester bond in the heated and melted state, when the amount of these catalysts added is reduced, the crosslinking reaction after adhesion becomes slow, and it takes a long time until the final adhesion strength is obtained. This caused problems such as the need for curing.
Japanese Patent Publication No. 51-30898 JP-A-4-227714 Japanese Patent Publication No.6-222956 Japanese Patent No. 2733180 JP 2001-11419 A Japanese Patent Publication No. 5-25917 JP 2000-212540 A Japanese Patent Laid-Open No. 7-3234 JP 2000-34459 A JP 2001-288366 A

  The present invention has been made in order to solve the above-mentioned problems in conventional silicone-based reactive hot melt adhesives, and is excellent in thermal stability during heating and melting, has a fast curing reaction after adhesion, An object of the present invention is to provide a silicone-based reactive hot-melt adhesive composition having excellent heat resistance.

In order to achieve the above object, as a result of intensive research, the present inventors, as a component of a reactive hot melt adhesive composition, have a hydrolyzable silyl group and a hydrolyzable silyl group. It has been found that the object of the present invention can be achieved by using a thermoplastic high molecular weight compound having at least one organic group in the molecule, which can act as a hydrolysis catalyst.
After that, when research was repeated aiming at further improvement of these effects, not only the hydrolyzable silyl group and the organic group having the catalytic action in the same molecule as the thermoplastic high molecular weight compound, but also urethane. When using a compound having one or more nitrogen atom-containing bonds selected from a bond, a thiourethane bond, a urea bond, a substituted urea bond, and a chemical bond derived from a Michael addition reaction, the effect is particularly noticeable. I started.

  That is, the present invention includes a hydrolyzable silyl group (A), an organic group (B) that can act as a hydrolysis catalyst for the silyl group (A), a urethane bond, a thiourethane bond, a urea bond, and a substituted urea bond. And a reactive hot melt adhesive composition comprising a thermoplastic high molecular weight compound (compound D) having in its molecule one or more nitrogen atom-containing bonds (C) selected from chemical bonds derived from Michael addition reactions. To do.

In the reactive hot melt adhesive composition of the present invention, the thermoplastic high molecular weight compound (compound D) is a thermoplastic high molecular weight compound (compound E) having the hydrolyzable silyl group (A) in the molecule. And a compound having the above-mentioned nitrogen atom-containing bond (C) in the molecule, and a compound having the organic group (B) in the molecule (compound B ′). To do.
In the reactive hot melt adhesive composition of the present invention, the thermoplastic high molecular weight compound (compound D) comprises the thermoplastic high molecular weight compound (compound F) having the organic group (B) in the molecule, and It is obtained by reacting a compound (compound A ′) having a hydrolyzable silyl group (A) in the molecule, and has a nitrogen atom-containing bond (C) in the molecule. To do.
In the reactive hot melt adhesive composition of the present invention, the thermoplastic high molecular weight compound (compound D) contains both the hydrolyzable silyl group (A) and the organic group (B) in the molecule. It is a compound obtained by reacting a thermoplastic high molecular weight compound (compound G) that does not have, the compound A ′ and the compound B ′, and having the nitrogen atom-containing bond (C) in the molecule. It is characterized by that.
In the reactive hot melt adhesive composition of the present invention, the thermoplastic high molecular weight compound (compound D) includes both the compound G, the hydrolyzable silyl group (A), and the organic group (B). It is obtained by reacting with a compound (compound H) having a hydrogen atom in the molecule, and has the nitrogen atom-containing bond (C) in the molecule.
The reactive hot melt adhesive composition of the present invention is characterized in that the hydrolyzable silyl group (A) is an alkoxysilyl group (X) represented by the following general formula (1).
-Si (R ¹ ) _n (R ² ) _3-n (1)
(However, R ¹ is an alkoxy group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 3).
In the reactive hot melt adhesive composition of the present invention, the organic group (B) is a basic organic group (Y) containing a tertiary amino group or an acidic organic group (Z) containing a carboxyl group. It is characterized by being.

  By using the thermoplastic high molecular weight compound of the present invention as an essential component, it is excellent in thermal stability at the time of heating and melting, has a fast curing reaction at room temperature, and has excellent heat resistance of the film after curing. A composition for hot melt adhesive is obtained.

  The greatest advantage of using the reactive hot melt adhesive composition of the present invention is that the hydrolyzable silyl group and the organic group having hydrolysis catalysis are present in the molecule of the same thermoplastic compound, and the hydrolysis is carried out. It is to selectively promote only the hydrolysis and crosslinking reaction with hydrolyzable silyl groups and to suppress the hydrolysis of ester bonds at the same time by bonding the organic group having a catalytic action to a high molecular weight thermoplastic compound. . This means that after bonding, that is, after the adhesive has cooled and solidified, a rapid curing reaction, that is, a rapid expression of the adhesive strength can be obtained, while in the heat-melted state, polymer main chain breakage, etc. It means that it is difficult to cause a decrease in thermal stability during heating and melting.

  In the present invention, various thermoplastic high molecular weight compounds are used, and the compound is a compound having a molecular weight of 1,000 to 100,000 which decreases in viscosity upon heating and further softens and / or melts. Point to. When the compound has a molecular weight of less than 1,000, it is difficult to obtain the effect of the present invention because evaporation and air diffusing easily occur when placed in a heated state. On the other hand, in the case of a compound having a molecular weight exceeding 100,000, it is not melted even in a heated state or has a high viscosity even when melted, and an industrially useful reactive hot-melt adhesive composition can be obtained. It becomes difficult.

The thermoplastic high molecular weight compound (compound D), which is one component of the composition of the present invention, has one or more hydrolyzable silyl groups (A) and organic groups (B) in the molecule. the hydrolyzable silyl group (a), conventionally known materials having the formula -Si-OR, -Si-Cl, -Si-NCO, -Si-NR 2, the -Si-O- (CO) -R bonds such as The group of is mentioned. Of these, the alkoxysilyl group (X) represented by the following general formula (1) is particularly suitable in consideration of the curing speed, industrial availability, and the like.
-Si (R ¹ ) _n (R ² ) _3-n (1)
In the general formula (1), R ¹ is an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, particularly preferably 1 or 2 carbon atoms, and R ² is 1 to 6 carbon atoms, preferably a carbon number. 1 to 3, particularly preferably an alkyl group having 1 or 2 carbon atoms, and n represents an integer of 1 to 3.

As the organic group (B), those having basic catalytic action include primary amino group, secondary amino group, tertiary amino group, quaternary amino group, quaternary amino group and counter anion. A group consisting of: an imino group (a group obtained by dehydration condensation of a primary amino group and a ketone or an aldehyde), an oxazolidino group (a group obtained by dehydration condensation of an N-alkyl-N-ethanolamino group and a ketone) ) And the like. In addition to these groups, urethane bonds, thiourethane bonds, urea bonds, and substituted urea bonds also exhibit sufficient catalytic activity in the present invention. Therefore, in the present invention, these bonds are included in the tertiary amino group. . Hereinafter, the urethane bond and the thiourethane bond may be collectively referred to as a (thio) urethane bond, and the urea bond and the substituted urea bond may be collectively referred to as a (substituted) urea bond.
In addition, as those having acidic catalytic action, carboxyl group, sulfonyl group, hydroxybenzyl group, phosphoryl group (residue of acidic phosphoric acid), nitrile group (residue of nitric acid), titanate group (residue of titanic acid), Examples thereof include an organic group containing a borate group (residue of boric acid) and the like. Among them, a basic organic group having a tertiary amino group has a wide range of reactivity and is easy to react when producing the compound D, considering industrial availability. (Y) or an acidic organic group (Z) containing a carboxyl group is particularly suitable.

Further, the compound D has at least one bond selected from a nitrogen atom-containing bond selected from a urethane bond, a thiourethane bond, a urea bond, a substituted urea bond, and a chemical bond derived from a Michael addition reaction in the molecule. Although it is a compound, it is particularly preferable that these bonds exist in the vicinity of the hydrolyzable silyl group (A) and the organic group (B) because the effects of the present invention can be maximized.
The reason is considered to be due to a phenomenon similar to the “hard / soft segment theory” generally known in polyurethane resins. The “hard / soft segment theory” is an idea that the urethane bond or urea bond of the polyurethane resin forms a microphase separation domain as a hard segment. That is, the same microphase-separated domain formation phenomenon occurs in the compound C of the present invention due to the highly polar (thio) urethane bond, (substituted) urea bond and the nitrogen atom derived from the Michael addition reaction. In addition, the hydrolyzable silyl group (A) and the organic group (B) present in the vicinity of these bonds and the like are also likely to gather together, and the effect of the present invention is considered to be more remarkable.

  Further, if these nitrogen atom-containing bonds are present in the vicinity of the hydrolyzable silyl group (A) and / or the organic group (B), a particularly remarkable effect can be obtained. The vicinity here means that the chain length from the hydrolyzable silyl group (A) or the organic group (B) to the nearest nitrogen atom-containing bond is 20 or less in carbon number. However, this chain may contain nitrogen atoms or oxygen atoms.

The compound D can be produced by the methods as listed in the following (1) to (4).
(1) A method of reacting the thermoplastic high molecular weight compound (compound E) having the hydrolyzable silyl group (A) in the molecule with the compound (compound B ′) having the organic group (B) in the molecule. (Manufacturing method 1).
(2) A method of reacting the thermoplastic high molecular weight compound (compound F) having the organic group (B) in the molecule with the compound having the hydrolyzable silyl group (A) (compound A ′) in the molecule. (Manufacturing method 2).
(3) A method in which the compound A ′ and the compound B ′ are reacted with a thermoplastic high molecular weight compound (compound G) (production method 3).
(4) A method of reacting the compound G (compound H) having the hydrolyzable silyl group (A) and the organic group (B) with the compound G (production method 4).

  Hereafter, each said manufacturing method is described in detail. In addition, the monomer which has a polymerizable unsaturated double bond used in each manufacturing method refers to the whole monomer which has the general carbon-carbon double bond which can be polymerized by radical polymerization. Examples thereof include α-olefins such as ethylene, propylene and 1-butene, dienes such as butadiene and isoprene, fatty acid vinyls such as vinyl acetate and propylene acid, unsaturated fatty acids such as acrylic acid and methacrylic acid, methyl Acrylic esters such as acrylate, ethyl acrylate, propyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, α, β- such as maleic acid, maleic anhydride and succinic acid Unsaturated dicarboxylic acids or their anhydrides, vinyl halides such as vinyl chloride and vinyl bromide, vinylidene halides such as vinylidene chloride, aromatic vinyls such as styrene and α-methylstyrene, and nitriles such as acrylonitrile Acrylamides such as N-methylacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, N-methylmethacrylamide, N-methylolmethacrylamide, N, N-dimethylmethacrylamide , Methacrylamides such as N, N-dimethylaminopropyl methacrylamide, and allyl compounds such as allyl sulfonate and allylamine. These compounds are not limited to one type, and two or more types can be used.

Manufacturing method 1
Production Method 1 comprises a method of reacting Compound E and Compound B ′.
As the compound E, an organic group used for the reaction between the hydrolyzable silyl group (A) and the compound B ′, for example, allyl group, acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, isocyanate group , Compounds having at least one group selected from an isothiocyanate group, a secondary amino group, a primary amino group and the like in the same molecule.
The compound E is exemplified by the compound produced by the following production method, but it goes without saying that the compound E is not limited thereto. In the following, acryloyl (group) and methacryloyl (group) are collectively referred to as (meth) acryloyl (group), and acrylamide (group) and methacrylamide (group) are collectively referred to as (meth) acrylamide (group). The isocyanate (group) and the isothiocyanate (group) may be collectively referred to as iso (thio) cyanate (group) (these are common in the following production methods 2 to 4).

(I) Compound having allyl group and hydrolyzable silyl group in the same molecule (a) Allyl group and hydroxyl group obtained by polymerization of oxyalkylene such as ethylene oxide and propylene oxide using allyl alcohol as a starting material An allyl group-terminated silyl group-containing polyoxyalkylene polymer obtained by reacting the containing polyoxyalkylene with an isocyanate silane having an equivalent or less equivalent to the hydroxyl group,
(B) Terminal iso (thio) cyanate (pre) polymer obtained by reacting polyol compound or polythiol compound with an excess amount of polyiso (thio) cyanate monomer with respect to these compounds, active hydrogen such as allyl alcohol, and allyl An allyl group-containing partially silylated (thio) urethane (pre) polymer obtained by reacting a compound having a group with a hydrolyzable silyl group-containing compound such as aminosilane or mercaptosilane,
(C) an allyl group-terminated iso (thio) cyanate (pre) polymer obtained by reacting a polyol compound or a polythiol compound with an excess of polyiso (thio) cyanate monomer and allyliso (thio) cyanate with respect to these compounds; An allyl group-containing partially silylated (thio) urethane (pre) polymer obtained by reacting a hydrolyzable silyl group-containing compound such as aminosilane or mercaptosilane.

(Ii) Compound having (meth) acryloyl group and / or (meth) acrylamide group and hydrolyzable silyl group in the same molecule (a) (meth) acrylic acid ester monomer and / or (meth) acrylamide monomer, di A (meth) acryloyl group and / or a (meth) acrylamide group and a silyl group obtained by copolymerizing a (meth) acrylic monomer and / or a di (meth) acrylamide monomer with (meth) acrylic silane, mercaptosilane, etc. Containing (meth) acrylic polymer,
(B) Hydrolysis of terminal iso (thio) cyanate (pre) polymer obtained by reacting polyol compound or polythiol compound with an excess amount of polyiso (thio) cyanate monomer with respect to these compounds, and aminosilane, mercaptosilane, etc. An iso (thio) cyanate group-containing partially silylated (thio) urethane (pre) polymer obtained by reacting a reactive silyl group-containing compound with a hydroxy (meth) acrylate monomer and / or a hydroxy (meth) acrylamide monomer A silylated (thio) urethane (pre) polymer partially containing (meth) acryloyl groups and / or (meth) acrylamide groups,
(C) radical copolymerization of a monomer having a polymerizable unsaturated double bond and a monomer having a polymerizable unsaturated double bond and a hydrolyzable silyl group, and then a halogenated (meth) acryloyl group and / or halogen. A vinyl polymer containing a (meth) acryloyl group and / or a (meth) acrylamide group and a silyl group at the terminal, obtained by reacting a compound having a modified (meth) acrylamide group.

(Iii) A compound having an iso (thio) cyanate group and a hydrolyzable silyl group in the same molecule (a) A polyol compound or a polythiol compound is reacted with an excess amount of a polyiso (thio) cyanate monomer with respect to these compounds. Iso (thio) cyanate (pre) polymer obtained by reacting with a hydrolyzable silyl group-containing compound such as aminosilane, mercaptosilane and the like in an equivalent amount with respect to the iso (thio) cyanate group. ) Cyanate group-containing partially silylated (thio) urethane (pre) polymer,
(B) A hydrolyzable silyl group-containing polyol or polythiol obtained by reacting a polyol compound or polythiol compound with less than an equivalent amount of iso (thio) cyanate silane with respect to a hydroxyl group or a mercapto group, and a polyiso (thio) cyanate monomer Hydrolyzable silyl group-containing iso (thio) cyanate urethane (pre) polymer obtained by reaction.

(Iv) A compound having an amino group (secondary amino group or primary amino group) and a hydrolyzable silyl group in the same molecule (a) An amine-modified polymer containing an amino group at the terminal or side chain of the molecule And an amino group- and silyl group-containing polymer obtained by reacting less than an equivalent amount of isocyanate silane with respect to the amino group.

  As the compound B ′, groups used for the reaction between the organic group (B) and the compound (E), that is, mercapto group, butadienyl group, secondary amino group, primary amino group, hydroxyl group, ( The compound which has at least 1 sort (s) of organic group chosen from a (meth) acryloyl group, a (meth) acrylamide group, etc. in the same molecule is mentioned.

Among these compounds, the organic group (Y) containing a tertiary amino group as the organic group (B).
Particularly preferred are compounds having a compound (compound Y ′) having a carboxyl group and an organic group (Z) having a carboxyl group (compound Z ′) in the molecule.

  Compound Y ′ includes, for example, mercapto groups such as mercaptoamine, 2-amino-5-mercapto-1,3,4-thiazole, aminothiophenol, mercaptopurine, 2-mercaptobenzimidazole, and 2-mercaptobenzothiazole. Amine compounds; Butadienyl group-containing amine compounds such as 2-amino-1,3-butadiene; ethylamine, allylamine, isopropylamine, 2-ethylhexylamine, 2-ethylhexyloxypropylamine, 3-ethoxypropylamine, 3- (diethylamino) Propylamine, 3- (dibutylamino) propylamine, t-butylamine, sec-butylamine, propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, stearylamine, 2-phenyl Primary amino group and / or secondary amino such as nylethylamine, N-phenyl-γ-aminopropyltrimethoxysilane, various imidazole compounds, aminophenol, 1- (2-hydroxyethyl) piperazine, hydroxydiphenylamine, diallylamine Group-containing compounds: N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldi Ethoxysilane, these other special aminosilanes manufactured by Shin-Etsu Chemical Co., Ltd., trade names: KBM6063, X-12-896, KBM576, X-12-565, X-12-580, X-12-5263, KBM6123, X -12-575, X-12-562, X-12-52 02, X-12-5204, KBE9703, manufactured by Asahi Kasei Wacker Silicone Co., Ltd., trade names: SLJ7502, SLJ7503 and other silyl group-containing amine compounds; Sankyo Air Products DABCO-T (registered trademark) manufactured by Nippon Fine Chemical Co., Ltd. , Trade Name: Hydroxyl-containing amine compounds such as L-prolinol, L-alaninol, L-valinol; N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meta ) (Meth) acryloyl group-containing amine compounds such as acrylate and (meth) acryloylmorpholine; N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N , N-die Le (meth) acrylamide, (meth) acrylamide group-containing amine compound, and the like.

  Compound Z ′ includes mercapto group-containing carboxylic acid compounds such as mercaptoacetic acid, mercaptosuccinic acid and β-mercaptopropionic acid; butadienyl group-containing carboxylic acid compounds such as 1,3-butadiene-2-carboxylic acid; DL-allylglycine Amino acid compounds such as DL-serine, 2-amino-3-hydroxybenzoic acid, DL-phenylalanine, DL-leucine, β-alanine, DL-aspartic acid; hydrocortisone succinate, hydrocortisone acetate, dihydroxybenzoic acid, dihydroxycinnamic acid Examples thereof include hydroxyl group-containing carboxylic acid compounds such as acid, dimethylolpropionic acid, hydroxyoleic acid, hydroxyoctanoic acid, hydroxyacetic acid and hydroxystearic acid.

  A conventionally known reaction method can be employed for the reaction between the compound E and the compound B ′. Although the combination of both compounds in those reactions is illustrated in Table 1, it is not limited to these combinations. Among the combinations shown in Table 1, (a) a compound E having an organic group selected from an isocyanate group and an isothiocyanate group, and an organic group selected from a hydroxyl group, a mercapto group, a primary amino group, and a secondary amino group. (B) a compound E having an organic group selected from a primary amino group and a secondary amino group, and an organic group selected from a (meth) acryloyl group and a (meth) acrylamide group. (C) a compound E having an organic group selected from a (meth) acryloyl group and a (meth) acrylamide group, and an organic group selected from a primary amino group and a secondary amino group. Since the combination with the compound B ′ has a nitrogen atom-containing bond in the vicinity of the hydrolyzable silyl group (A) and / or the organic group (B) It is suitable for.

  In the reaction of Compound E and Compound B ′, the reactive group in Compound B ′ is 0.1 to 1.5 mol, preferably 0.3 to 1. Both are carried out using 2 mol, more preferably 0.5 to 1.0 mol. The reaction is usually carried out at 50 to 150 ° C. for 1 to 10 hours.

Manufacturing method 2
Production method 2 comprises a method of reacting compound E with compound A ′.
As the compound F, an organic group used for the reaction between the organic group (B) and the compound A ′, for example, an allyl group, a (meth) acryloyl group, a (meth) acrylamide group, an isocyanate group, an isothiocyanate group, Examples thereof include compounds having at least one group selected from a secondary amino group, a primary amino group, a mercapto group, a hydroxyl group, a carboxyl group and the like in the same molecule. Of the organic groups (B), an organic group (Y) containing a tertiary amino group or an organic group (Z) containing a carboxyl group is particularly preferred.
The compound F is exemplified by the compound produced by the following production method, but it goes without saying that the compound F is not limited thereto.

(I) Compound having allyl group and organic group (Y) in the same molecule
(A) Terminal iso (thio) cyanate (pre) polymer obtained by reacting a polyol compound or polythiol compound with an excess amount of polyiso (thio) cyanate monomer with respect to these compounds, and alkyl alkanolamine, alkylamine, etc. An amino group and an allyl group-containing (thio) urethane (pre) polymer obtained by reacting an active hydrogen or amino group-containing compound with an allyl group-containing compound such as allylamine.

(Ii) a compound having a (meth) acryloyl group and / or a (meth) acrylamide group and an organic group (Y) in the same molecule (a) a monomer having a polymerizable unsaturated double bond; A halogen having a halogenated (meth) acryloyl group and / or a halogenated (meth) acrylamide group after radical copolymerization with a monomer having a heavy bond and a tertiary amino group and / or an amino group-containing compound such as mercaptoamine. (Meth) acrylic group and / or (meth) acrylamide group terminal amino group-containing vinyl polymer obtained by reacting the compound,
(B) Terminal iso (thio) cyanate (pre) polymer obtained by reacting a polyol compound or polythiol compound with an excess amount of polyiso (thio) cyanate monomer with respect to these compounds, such as alkyl alkanolamine or alkylamine An active hydrogen and / or amino group-containing compound is reacted with an active hydrogen-containing (meth) acrylate compound such as hydroxy (meth) acrylate and / or hydroxy (meth) acrylamide and / or an active hydrogen-containing (meth) acrylamide compound. The amino group and (meth) acrylic group and / or (meth) acrylamide group-containing (thio) urethane (pre) polymer obtained.

(Iii) A compound having an iso (thio) cyanate group and an organic group (Y) in the same molecule (i) A polyol compound or a polythiol compound is reacted with an excess amount of a polyiso (thio) cyanate monomer with respect to those compounds. It is obtained by reacting the terminal iso (thio) cyanate (pre) polymer obtained in this way with a compound having an active hydrogen and / or amino group such as an alkylalkanolamine or alkylamine of less than an equivalent amount relative to the (thio) isocyanate group. Amino group-containing (thio) urethane (pre) polymer,
(B) A hydroxyl group-containing polyoxyalkylene obtained by polymerizing oxyalkylenes such as ethylene oxide and propylene oxide with alkylalkanolamine as a starting material is reacted with a polyiso (thio) cyanate monomer having an equivalent weight or less with respect to the hydroxyl group. An iso (thio) cyanate group-terminal amino group-containing polyoxyalkylene polymer obtained by
(C) Michael addition of a monomer having a polymerizable unsaturated double bond of less than an equivalent amount to the amino group to an amine-modified polymer containing an amino group at the terminal or side chain of the molecule, An amino group-containing (thio) urethane (pre) polymer obtained by reacting a (thio) cyanate monomer.

(Iv) A compound having a secondary amino group or a primary amino group and an organic group (Y) in the same molecule (a) An amine-modified polymer containing an amino group at the terminal or side chain of the molecule, A tertiary amino group-containing amine-modified polymer obtained by Michael addition of a monomer having a polymerizable unsaturated double bond of less than equivalent to
(B) a monomer having a polymerizable unsaturated double bond, a monomer having a polymerizable unsaturated double bond and a tertiary amino group, a polymerizable unsaturated double bond and a primary amino group, and / or Vinyl containing primary amino group and / or secondary amino group and tertiary amino group obtained by radical copolymerization of monomer having secondary amino group and / or amino group-containing compound such as mercaptoamine Polymer.

(V) A compound having a mercapto group or a hydroxyl group and an organic group (Y) in the same molecule (a) A hydroxyl group obtained by polymerizing oxyalkylene such as ethylene oxide or propylene oxide using an alkylalkanolamine as a starting material Terminal amino group-containing polyoxyalkylene polymer,
(B) a terminal iso (thio) cyanate (pre) polymer obtained by reacting a polyol compound or a polythiol compound with an excess amount of a polyiso (thio) cyanate monomer relative to these compounds, and a (thio) isocyanate group A compound having a hydroxyl group and / or a mercapto group and an amino group obtained by reacting a compound having an active hydrogen and / or amino group such as an alkyl alkanolamine or alkylamine with less than an equivalent amount with a hydroxyl group and / or mercapto group-containing compound (thio ) Urethane (pre) polymer,
(C) radical copolymerization of a monomer having a polymerizable unsaturated double bond, a monomer having a polymerizable unsaturated double bond and a hydroxyl group, a monomer having a polymerizable unsaturated double bond and a tertiary amino group, etc. Hydroxyl group and tertiary amino group-containing vinyl polymer obtained by the process.

(Vi) A compound having a carboxyl group and an organic group (Y) in the same molecule (a) An amine-modified polymer containing a secondary amino group or a primary amino group at the terminal or side chain of the molecule (meta ) Amino group and carboxyl group-containing polymer obtained by Michael addition of acrylic acid monomer, etc.
(B) a monomer having a polymerizable unsaturated double bond, a monomer having a polymerizable unsaturated double bond and a secondary amino group or primary amino group, and / or an amino group-containing compound such as mercaptoamine, An amino group- and carboxyl group-containing vinyl polymer obtained by radical copolymerization of a (meth) acrylic acid monomer or the like.

(Vii) Compound having an allyl group and an organic group (Z) in the same molecule
(A) Terminal iso (thio) cyanate (pre) polymer obtained by reacting a polyol compound or polythiol compound with an excess amount of polyiso (thio) cyanate monomer with respect to these compounds, and activities such as alkanol carboxylic acid and amino acid A carboxyl group and an allyl group-containing (thio) urethane (pre) polymer obtained by reacting a compound having hydrogen and a carboxyl group with an allyl group-containing compound such as allylamine;
(B) Allyl alcohol or the like as a starting material, and after polymerization of oxyalkylene such as ethylene oxide and propylene oxide, the allyl group-terminated polyoxyalkylene polymer obtained by reacting allyl halide is converted to mercaptoacetic acid or the like. An allyl group-terminated carboxyl group-containing polyoxyalkylene polymer obtained by reacting a compound having an allyl group and a carboxyl group.

(Viii) a compound having a (meth) acryloyl group and / or a (meth) acrylamide group and an organic group (Z) in the same molecule (a) a monomer having a polymerizable unsaturated double bond, and a polymerizable unsaturated dimer (Meth) acryloyl group and / or (meth) acrylamide group obtained by radical copolymerization of a monomer having a heavy bond and a carboxyl group with di (meth) acryl monomer and / or di (meth) acrylamide monomer A vinyl polymer having a carboxyl group,
(B) After radical copolymerization of a monomer having a polymerizable unsaturated double bond and a monomer having a polymerizable unsaturated double bond and a carboxyl group, a halogenated (meth) acryloyl group and / or a halogenated (meta ) A vinyl polymer containing a (meth) acryloyl group and / or a (meth) acrylamide group-terminated carboxyl group obtained by reacting a halogen compound having an acrylamide group.

(Ix) A compound having an iso (thio) cyanate group and an organic group (Z) in the same molecule (a) A polyol compound or a polythiol compound is reacted with an excess amount of a polyiso (thio) cyanate monomer with respect to those compounds. A carboxyl group-containing product obtained by reacting a terminal iso (thio) cyanate (pre) polymer obtained by the above reaction with an active hydrogen such as alkanol carboxylic acid or amino acid and a carboxyl group-containing compound with less than an equivalent amount to the (thio) isocyanate group ( Thio) urethane (pre) polymer.

(X) a compound having an amino group and an organic group (Z) in the same molecule (a) a monomer having a polymerizable unsaturated double bond, an amino group-containing compound such as mercaptoamine, and a (meth) acrylic acid monomer An amino group- and carboxyl group-containing vinyl polymer obtained by radical copolymerization of a monomer having a polymerizable unsaturated double bond and a carboxyl group such as

(Xi) A compound having a mercapto group or hydroxyl group and an organic group (Z) in the same molecule (a) A compound having an active hydrogen and carboxyl group such as alkanol carboxylic acid and amino acid and a polyiso (thio) cyanate monomer A carboxyl group-containing polyol compound or polythiol compound obtained by reacting a carboxyl group-containing modified iso (thio) cyanate compound obtained by reacting with a polyol compound or a polythiol compound,
(B) A monomer having a polymerizable unsaturated double bond, a monomer having a polymerizable unsaturated double bond and a hydroxyl group, and a monomer having a polymerizable unsaturated double bond and a carboxyl group such as a (meth) acrylic acid monomer An amino group- and carboxyl group-containing vinyl polymer obtained by radical copolymerization.

(Xii) a compound having a carboxyl group and an organic group (Z) in the same molecule (a) a carboxylic acid-modified polymer containing a carboxyl group at the end or side chain of the molecule,
(B) A carboxyl group-containing vinyl polymer obtained by radical copolymerization of a monomer having a polymerizable unsaturated double bond and a monomer having a polymerizable unsaturated double bond and a carboxyl group.

  As compound X ′, Shin-Etsu Chemical Co., Ltd., trade name: KBM573, KBM602, KBM603, KBE603, KBM903, KBE903, Chisso, trade name: Silaace XS1003 and other so-called aminosilanes, Shin-Etsu Chemical Co., Ltd., trade name : So-called epoxy silanes such as KBM303, KBM403, KBE402 and KBE403, manufactured by Shin-Etsu Chemical Co., Ltd., trade names: so-called (meth) acrylsilanes such as KBM502, KBM503, KBE502, KBE503 and KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd., products Name: so-called isocyanate silanes such as KBE9007, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: so-called vinyl silanes such as KBM1003, KBE1003, KBM1403, etc., manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM802, KB So-called mercaptosilanes such as 803 and the like.

  Further, modified aminosilanes, modified epoxy silanes, modified (meth) acryl silanes, modified isocyanate silanes, modified vinyl silanes, modified vinyl compounds obtained by previously reacting the above compound X ′ with compounds having other functional groups. Mercaptosilanes (hereinafter, these may be referred to as modified silane compounds) can also be used. By carrying out the above modification, it is possible to introduce the organic group (B) in the vicinity of the hydrolyzable silyl group (A), whereby the effects of the present invention can be obtained particularly remarkably. It is particularly preferable to use

  For the reaction between Compound F and Compound A ′, a conventionally known reaction method can be employed. The combinations of both compounds in these reactions are exemplified in Table 2, but are not limited to these combinations. Among the combinations shown in Table 2, (a) a combination of a compound F having an organic group selected from an isocyanate group and an isothiocyanate group and (modified) aminosilanes, (b) a (meth) acryloyl group and a (meth) acrylamide group A combination of a compound F having an organic group selected from (modified) aminosilanes or (modified) mercaptosilanes, (c) an organic group selected from mercapto groups, hydroxyl groups, primary amino groups and secondary amino groups And (d) a compound F having an organic group selected from primary amino groups and secondary amino groups and (modified) (meth) acrylsilanes. Whether the combination produces a nitrogen atom-containing bond in the vicinity of the hydrolyzable silyl group (A) and / or the organic group (B) It is particularly suitable.

  In the reaction of Compound F with Compound A ′, the reactive group in Compound A ′ is 0.1-1.5 mol, preferably 0.3-1. Both are carried out using 2 mol, more preferably 0.5 to 1.0 mol. The reaction is usually carried out at 50 to 150 ° C. for 1 to 10 hours.

Manufacturing method 3
Production method 3 comprises a method of reacting the compound A ′ and the compound B ′ with the compound G. As compound A ′, compounds used in production method 2 can be mentioned, and like production method 2, compound X ′ is particularly suitable. In addition, examples of the compound B ′ include compounds used in the production method 1. Like the production method 1, the compound Y ′ and the compound Z ′ are particularly suitable.

  The compound G includes at least one group selected from organic groups used for the reaction with the compound A ′ and the compound B ′, such as a hydroxyl group, a mercapto group, an iso (thio) cyanate group, an amino group, and a glycidyl group. And thermoplastic high molecular weight compounds in the molecule. Among these, considering that the object of the present invention is a reactive hot melt adhesive, (a) a polyester polyol having a main chain of a polyester skeleton and a hydroxyl group at the molecular end, and (b) a main chain of a styrene copolymer. Epoxy-modified SBR (styrene-butadiene copolymer rubber) having a glycidyl group in the side chain and (c) an amine-modified EVA having a main chain of ethylene-vinyl acetate polymer (EVA) and having an amino group in the side chain Are preferable because they are solid at room temperature. In addition to these, a terminal polyiso (thio) cyanate (pre) polymer obtained by reacting (d) a polyol compound or a polythiol compound with an excess amount of a polyiso (thio) cyanate compound monomer with respect to these compounds is also a preferred compound. is there.

  For the reaction of Compound A ′ and Compound B ′ with Compound G, conventionally known reaction methods can be employed. The combinations of Compound A ′ and Compound B ′ and Compound G in these reactions are exemplified in Table 3, but are not limited to these combinations. Among the combinations shown in Table 3, (a) a combination of a compound G having an organic group selected from a hydroxyl group, a mercapto group and an amino group, and a compound A ′ and a compound B ′ having an iso (thio) cyanate group, (b) A combination of a compound G having an iso (thio) cyanate group and a compound A ′ and a compound B ′ having an organic group selected from a hydroxyl group, a mercapto group and an amino group; (c) a compound G having an amino group and (meth) acryloyl A combination of a compound A ′ having a group and / or a (meth) acrylamide group and a compound B ′, and (d) a compound G having an (meth) acryloyl group and / or a (meth) acrylamide group and a compound A having an amino group ′ And Compound B ′ may contain a nitrogen atom in the vicinity of the hydrolyzable silyl group (A) and / or the organic group (B). It is particularly preferred because it produces a bond.

  In the reaction of compound A ′ and compound B ′ with compound G, the total of reactive groups in compound A ′ and compound B ′ is 0.1 to 1.5 per mole of reactive group in compound G. It is carried out by using three members so that the molar amount is preferably 0.3 to 1.2 mol, more preferably 0.5 to 1.0 mol. At this time, Compound A ′ and Compound B ′ may be used simultaneously and reacted with Compound G, or may be used individually and reacted with Compound G. The reaction is usually carried out at 50 to 150 ° C. for 1 to 10 hours.

Manufacturing method 4
Production Method 4 comprises a method of reacting Compound H and Compound G. This method is a particularly preferable method because the compound D, which is the target product, can be obtained by a one-step reaction. Compound G may be the same as Compound G used in Production Method 3.

  As the compound H, an organic group used for the reaction between the hydrolyzable silyl group (A) and the compound G, for example, a hydroxyl group, a mercapto group, an iso (thio) cyanate group, an amino group, a glycidyl group, an acryloyl group, The compound which has at least 1 type of group chosen from a (meth) acrylamide group etc. in a molecule | numerator is mentioned. As such a compound, the compounds exemplified as the above-mentioned compound X ′ can be used. Among them, a modified aminosilane obtained by reacting a commercially available so-called silane coupling agent with a compound having another functional group in advance. , Modified epoxy silanes, modified (meth) acryl silanes, modified isocyanate silanes, modified vinyl silanes, modified mercapto silanes can also be used. By performing the above modification, it is possible to introduce the organic group (B) in the vicinity of the hydrolyzable silyl group (A), and thereby the effects of the present invention can be obtained particularly remarkably. It is particularly preferable to use modified silanes. Among these modification methods, those using the Michael addition reaction and those using the (thio) urethane bond or (substituted) urea bond forming reaction are particularly preferable.

  For the reaction between Compound G and Compound H, a conventionally known reaction technique can be employed. The combinations of Compound F and Compound G in these reactions are exemplified in Table 4, but are not limited to these combinations. Among the combinations shown in Table 4, Compound G having an organic group selected from a hydroxyl group, a mercapto group, an iso (thio) cyanate group and an amino group, (modified) aminosilanes, (modified) epoxysilanes, (modified) (meta In particular, the combination with the compound H selected from acrylic silanes and (modified) isocyanate silanes generates a nitrogen atom-containing bond in the vicinity of the hydrolyzable silyl group (A) and / or the organic group (B). Is preferred.

  The reaction between compound H and compound G is carried out in such a manner that the reactive group in compound H is 0.1 to 1.5 mol, preferably 0.3 to 1.2 mol, relative to 1 mol of reactive group in compound G. Furthermore, it is carried out using both so that it may become 0.5-1.0 mol more preferably. The reaction is usually carried out at 50 to 150 ° C. for 1 to 10 hours.

  The reactive hot melt adhesive composition of the present invention contains the above compound D as an essential component, but contains a filler, a room temperature solidifying imparting agent, and various additives as necessary in addition to the component. Can do. The filler, room temperature solidification imparting agent, and various additives that can be included as necessary may be added to the prepared compound D or may be added when preparing the compound D.

  Examples of the filler that can be included as necessary include fumed silica, calcium carbonate, clay, talc, silica, and various balloons.

  The room temperature solidification imparting agent refers to a resin capable of solidifying the composition of the present invention by mixing with compound D having fluidity at room temperature when heated and cooling to room temperature. Examples of such a room temperature solidification imparting agent include rosin and hydrogenated rosin that is a derivative thereof, (hydrogenated) polymerized rosin, (hydrogenated) rosin glycerin ester, (hydrogenated) rosin pentaerythritol ester, and disproportionated rosin. Glycerin ester and disproportionated rosin pentaerythritol ester, (hydrogenated) terpene phenol resin, ketone resin, petroleum resin (aliphatic, aromatic, aliphatic-aromatic copolymer, alicyclic and their water Additives), (hydrogenated) terpene resins, coumarone-indene resins, so-called tackifiers such as phenol resins and xylene resins, styrene-isoprene-styrene block copolymers (SIS), styrene-butadiene-styrene block copolymers (SBS), styrene-ethylene-butylene-styrene block copolymer (S BS), styrene block copolymers such as styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), and hydrogenated products thereof, ethylene-ethyl acrylate copolymer Copolymers (EEA), acrylic copolymers such as ethylene-n-butyl acrylate copolymer (ENBA), ethylene copolymers such as ethylene-vinyl acetate copolymer (EVA), amorphous polyalphaolefin (APAO) And various thermoplastic polymers such as polyamide, polyester, polyacryl, and polyurethane. These room temperature solidification imparting agents are not limited to one type, and two or more types can be used.

Examples of various additives include plasticizers, additives, solvents, and dehydrating agents. Examples of the plasticizer include phthalates such as dioctyl phthalate and dibutyl phthalate, and fatty acid carboxylic acid esters such as dioctyl adipate and dibutyl sebacate.
Examples of the additive include an antioxidant, a thixotropic agent, an ultraviolet absorber, a pigment, various tackifiers, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and an epoxy such as bisphenol A type or bisphenol F type. Examples thereof include resins. As the silane coupling agent, aminosilane is particularly preferable.
As the solvent, any compound may be used as long as it is compatible with the compound D and has a moisture content of 500 ppm or less. However, considering that it is used in a heated and melted state, a high-boiling organic solvent is used. Is preferred.
Examples of the dehydrating agent include slaked lime, orthosilicate ester, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, various alkyl alkoxysilanes, various vinyl alkoxysilanes, and the like.

  Hereinafter, the present invention will be described in detail with reference to examples. In the following examples,% is based on mass.

(Synthesis Example 1) (Synthesis of Compound X ′)
Under a nitrogen atmosphere, 1,000 g of KBM603 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) γ-aminopropyltrimethoxysilane) was charged in a reaction vessel, and 775 g of methyl acrylate was added dropwise thereto while stirring. The compound was reacted while gradually warming to give compound X′-1.

(Synthesis Example 2) (Synthesis of Compound X ′)
In a nitrogen atmosphere, 1,000 g of KBM903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane) was charged in a reaction vessel, and while stirring, 456 g of methyl acrylate was added dropwise thereto while gradually heating. Reacted. Thereafter, 20 g of acrylic acid was further dropped and reacted while cooling with ice to obtain Compound X′-2.

(Synthesis Example 3) (Synthesis of Compound X ′)
Under a nitrogen atmosphere, 1,000 g of KBM903 was placed in a reaction vessel, and 480 g of methyl acrylate was added dropwise to the reaction vessel while stirring, and reacted while gradually heating. Thereafter, the compound obtained above was dropped into 1,240 g of Desmodule I (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., isophorone diisocyanate) charged in another reaction vessel in a nitrogen atmosphere, and stirred while cooling to room temperature. To give compound X′-3.

(Synthesis Example 4) (Synthesis of Compound X ′)
Under a nitrogen atmosphere, 600 g of N, N′-methylenebisacrylamide was charged into a reaction vessel, and while stirring, KBM573 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-γ-aminopropyltrimethoxysilane) 1,000 g Was added dropwise while cooling to room temperature, heated to 70 ° C. and reacted for 5 hours to obtain Compound X′-4.

Synthesis Example 5 (Synthesis of Compound X ′)
In a nitrogen atmosphere, 1,000 g of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane) and 5 g of triethylamine as a catalyst were charged in a reaction vessel, and 400 g of ethanedithiol was added to the reaction vessel at room temperature. The solution was added dropwise while cooling to 70 ° C., heated to 70 ° C., and reacted for 5 hours to obtain Compound X′-5.

(Synthesis Example 6) (Synthesis of Compound E)
Under a nitrogen atmosphere, 1,000 g of polyoxypropylene having an average molecular weight of 8,000 obtained by polymerization of propylene oxide using allyl alcohol as a starting material was charged in a reaction vessel, and Y-5187 (trade name, Nippon Unicar Company Limited) was added thereto. (Product, isocyanate silane) 26 g was reacted and added to obtain a compound E-1 comprising an allyl group and a silyl group-containing polyoxypropylene compound.

(Synthesis Example 7) (Synthesis of Compound E)
Under a nitrogen atmosphere, 1,000 g of Dynacol 7130 (trade name, manufactured by Degussa Japan Co., Ltd., polyester polyol) and 150 g of Desmodur I were charged and reacted in a reaction vessel, and the polyester had an NCO (isocyanate group) content of 2.2%. A main chain skeleton urethane prepolymer was obtained.
Further, 85 g of KBM573 and 20 g of allyl alcohol were reacted with this prepolymer to obtain a compound E-2 comprising an allyl group and silyl group-containing polyester.

(Synthesis Example 8) (Synthesis of Compound E)
The reaction was carried out in the same manner as in Synthesis Example 7 except that 20 g of allyl alcohol was changed to 40 g of 2-hydroxyethyl acrylate, thereby obtaining a compound E-3 comprising an acryloyl group- and silyl group-containing polyester.

(Synthesis Example 9) (Synthesis of Compound E)
Under a nitrogen atmosphere, 1,000 g of Dynacol 7130 and 150 g of Desmodur I were charged in a reaction vessel and reacted to obtain a polyester main chain skeleton urethane prepolymer having an NCO content of 2.2%.
Furthermore, 135g of compound X'-1 was made to react with this compound, and the compound E-4 which consists of an isocyanate group and silyl group containing polyester was obtained.

(Synthesis Example 10) (Synthesis of Compound E)
A compound E-5 comprising an isocyanate group- and silyl group-containing polyester was obtained by reacting in the same manner as in Synthesis Example 9 except that Compound X′-1 was changed to 85 g of KBM573.

(Synthesis Example 11) (Synthesis of Compound E)
Under a nitrogen atmosphere, 1,000 g of Jeffermine D-2000 (trade name, manufactured by Huntsman, Polyether Polyamine) and 395 g of Compound X′-4 were charged and reacted in a reaction vessel, and the amino group and silyl group-containing polyoxyalkylene were reacted. Compound E-6 consisting of

(Example 1) (Production method 1)
In a nitrogen atmosphere, 1,026 g of compound E-1 and 1,500 g of super ester A-100 (trade name, manufactured by Arakawa Chemical Co., Ltd., special rosin ester) were charged in a reaction vessel, and mercapto was stirred into this while being heated and melted. A composition containing Compound D was obtained by reacting 11.5 g of acetic acid. This compound D has a urethane bond in the molecule.

(Example 2) (Production method 1)
A composition containing Compound D was obtained by reacting in the same manner as in Example 1 except that mercaptoacetic acid was changed to 9.7 g of 2-aminoethanethiol. This compound D has a urethane bond in the molecule.

(Example 3) (Production Method 1)
Under a nitrogen atmosphere, 1,255 g of compound E-2 was charged into a reaction vessel, and 32 g of mercaptoacetic acid was reacted with this while stirring in a heated and melted state to obtain a composition containing compound D. This compound D has a urethane bond in the molecule.

(Example 4) (Production Method 1)
A composition containing Compound D was obtained by reacting in the same manner as in Example 3 except that mercaptoacetic acid was changed to 27 g of 2-aminoethanethiol. This compound D has a urethane bond in the molecule.

(Example 5) (Production Method 1)
A composition containing Compound D was obtained by reacting in the same manner as in Example 3 except that Compound E-2 was changed to 1,275 g of Compound E-3 and mercaptoacetic acid was changed to 25 g of t-butylamine. This compound D has a urethane bond, a substituted urea bond, and a chemical bond derived from Michael addition (hereinafter referred to as Michael addition bond) in the molecule.

(Example 6) (Production method 1)
A composition containing Compound D was obtained by reacting in the same manner as in Example 5 except that Compound E-3 was changed to 1,285 g of Compound E-4. This compound D has a urethane bond, a substituted urea bond and a Michael addition bond in the molecule.

(Example 7) (Production Method 1)
A composition containing Compound D was obtained by reacting in the same manner as in Example 3 except that Compound E-2 was changed to 1,235 g of Compound E-5 and mercaptoacetic acid was changed to 30 g of β-alanine. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 8) (Production method 1)
A composition containing Compound D was obtained by reacting in the same manner as in Example 7 except that β-alanine was changed to 25 g of t-butylamine. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 9) (Production method 1)
A composition containing Compound D was obtained by reacting in the same manner as in Example 1 except that Compound E-1 was changed to 1,225 g of Compound E-6 and mercaptoacetic acid was changed to 3 g of acrylic acid. This compound D has a Michael addition bond in the molecule.

(Synthesis Example 12) (Synthesis of Compound F)
Under a nitrogen atmosphere, 1,000 g of Dynacol 7130 and 150 g of Desmodur I were charged in a reaction vessel and reacted to obtain a polyester main chain skeleton urethane prepolymer having an NCO content of 2.2%.
Furthermore, 25 g of t-butylamine was reacted with this prepolymer to obtain a compound F-1 comprising an amino group- and isocyanate group-containing polyester.

(Synthesis Example 13) (Synthesis of Compound F)
Under a nitrogen atmosphere, 1,000 g of Dynacol 7130 and 150 g of Desmodur I were charged in a reaction vessel and reacted to obtain a polyester main chain skeleton urethane prepolymer having an NCO content of 2.2%.
Furthermore, 12 g of ethyldiethanolamine was reacted with this prepolymer, and then 17 g of 2-hydroxyethyl acrylate and 17 g of methanol were reacted to obtain a compound F-2 comprising an amino group- and acryloyl group-containing polyester.

(Synthesis Example 14) (Synthesis of Compound F)
In a nitrogen atmosphere, 1 liter of toluene was charged in a reaction vessel, and while stirring at 100 ° C., 400 g of methyl methacrylate (MMA), 400 g of n-butyl acrylate (BA), 100 g of 2-hydroxyethyl acrylate (HEA), ACMO (Product name, manufactured by Kojin Co., Ltd., acryloylmorpholine) 100 g, 20 g of azobisisobutyronitrile (AIBN) as a polymerization initiator, and 25 g of dodecyl mercaptan as a chain transfer agent are dropped over 5 hours, and a polymerization reaction is performed. Went. Thereafter, toluene as a solvent was distilled off by heating under reduced pressure to obtain Compound F-3 comprising an amino group- and hydroxyl group-containing acrylic resin.

(Synthesis Example 15) (Synthesis of Compound F)
Except for changing ACMO to 100 g of acrylic acid, the reaction was carried out in the same manner as in Synthesis Example 14 to obtain a compound F-4 comprising a carboxyl group- and hydroxyl group-containing acrylic resin.

(Synthesis Example 16) (Synthesis of Compound F)
Under a nitrogen atmosphere, 1,000 g of Dynacol 7130 and 150 g of Desmodur I were charged in a reaction vessel and reacted to obtain a polyester main chain skeleton urethane prepolymer having an NCO content of 2.2%.
Furthermore, this prepolymer was reacted with 30 g of β-alanine to obtain a compound F-5 comprising a carboxy group-containing and isocyanate group-containing polyester.

(Synthesis Example 17) (Synthesis of Compound F)
Under a nitrogen atmosphere, 1,000 g of polyoxypropylene having an average molecular weight of 4,000 with allyl groups introduced into 97% of all molecular terminals in a reaction vessel was charged, 20 g of mercaptoacetic acid was reacted and added thereto, and carboxyl groups and allyl groups were added. Compound F-6 consisting of the containing polyoxyalkylene was obtained.

(Example 10) (Production method 2)
In a nitrogen atmosphere, 1,175 g of compound F-1 was charged into a reaction vessel, and SILQUEST A-Link15 (trade name, N-ethyl-aminoisobutyltrimethoxysilane, manufactured by Nihon Unicar Company) was added to the reaction vessel while stirring in a molten state. 75 g of reaction was performed to obtain a composition containing Compound D. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 11) (Production method 2)
Compound F-1 was reacted in the same manner as in Example 10 except that 1,196 g of compound F-2 and the amount of SILQUEST A-Link15 used was changed to 35 g to obtain a composition containing compound D. This compound D has a urethane bond and a Michael addition bond in the molecule.

(Example 12) (Production method 2)
Under a nitrogen atmosphere, 1,000 g of SBU polyol 0807 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., amino group-containing polyoxypropylene polyol) and 1,500 g of superester A-100 are charged in a reaction vessel and stirred in a heated and melted state. While this was reacted with 410 g of Y-5187, a composition containing Compound D was obtained. This compound D has a urethane bond in the molecule.

(Example 13) (Production method 2)
A composition containing Compound D was obtained by reacting in the same manner as in Example 12 except that Y-5187 was changed to 975 g of Compound X′-3. This compound D has a urethane bond and a Michael addition bond in the molecule.

(Example 14) (Production method 2)
A composition containing Compound D was obtained by reacting in the same manner as in Example 10 except that Compound F-1 was changed to 1,000 g of Compound F-3 and SILQUEST A-Link15 was changed to 150 g of Y-5187. . This compound D has a urethane bond in the molecule.

(Example 15) (Production method 2)
A composition containing Compound D was obtained by reacting in the same manner as in Example 14 except that Compound F-3 was changed to 1,000 g of Compound F-4. This compound D has a urethane bond in the molecule.

Example 16 (Production Method 2)
A composition containing Compound D was obtained by reacting in the same manner as in Example 10 except that Compound F-1 was changed to 1,180 g of Compound F-5. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 17) (Manufacturing method 2)
Under a nitrogen atmosphere, 1,020 g of compound F-6 was charged in a reaction vessel, and 85 g of compound X′-5 was reacted with this while stirring. Thereafter, 1,500 g of Superester A-100 was added while stirring in a heated and melted state to obtain a composition containing Compound D. This compound D has a thiourethane bond in the molecule.

(Synthesis Example 18) (Synthesis of Compound G)
Under a nitrogen atmosphere, 1,000 g of Dynacol 7130 and 150 g of Desmodur I were charged in a reaction vessel and reacted to obtain a compound G-1 composed of an isocyanate group-containing polyester having an NCO content of 2.2%.

(Synthesis Example 19) (Synthesis of Compound G)
Under a nitrogen atmosphere, 1,000 g of PTMG3000 (trade name, manufactured by Mitsubishi Chemical Corporation, polyether polyol), Desmodur W (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., hydride of 4,4'-diphenylmethane diisocyanate) in a nitrogen atmosphere Was added and reacted to obtain a compound G-2 comprising an isocyanate group-containing polyether having an NCO content of 2.1%.

(Synthesis Example 20) (Synthesis of Compound G)
Under a nitrogen atmosphere, 1000 g of HPVM2203 (trade name, manufactured by Shell Japan, polyolefin polyol) and 125 g of XDI (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd., xylylene diisocyanate) were charged into the reaction vessel and reacted, and the NCO content was Compound G-3 consisting of 2.2% isocyanate group-containing polyolefin was obtained. Thereafter, 1,500 g of Superester A-100 was added while stirring in a heated and melted state to obtain a composition containing Compound G-3.

(Synthesis Example 21) (Synthesis of Compound G)
Under a nitrogen atmosphere, 1,000 g of PCDL L6002 (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd., polycarbonate polyol), EEA A-709 (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene-ethyl acrylate copolymer) in a reaction vessel. Of 300 g and 100 g of Superester A-100 were melt-kneaded while stirring at 120 ° C. to obtain a composition containing Compound G-4.

(Synthesis Example 22) (Synthesis of Compound G)
In a nitrogen atmosphere, 1 liter of toluene was charged in a reaction vessel, and while stirring at 100 ° C., a mixture of 400 g of BA, 100 g of HEA, 500 g of MMA, 20 g of AIBN as a polymerization initiator, and 25 g of dodecyl mercaptan as a chain transfer agent was taken over 5 hours. The solution was added dropwise to carry out a polymerization reaction. Thereafter, toluene as a solvent was distilled off by heating under reduced pressure to obtain a compound G-5 composed of a hydroxyl group-containing acrylic resin.

(Synthesis Example 23) (Synthesis of Compound G)
Under a nitrogen atmosphere, 1,000 g of Jeffermine D-2000 and 1,500 g of Superester A-100 were charged in a reaction vessel, and melt kneaded while stirring at 120 ° C. to obtain a composition containing Compound G-6.

(Synthesis Example 24) (Synthesis of Compound G)
Under a nitrogen atmosphere, 1,000 g of thiocol LP282 (trade name, manufactured by Toraythiol Co., Ltd., sulfur-containing polyoxyalkylene polythiol) and 1,500 g of superester A-100 were charged in a reaction vessel and melt-kneaded while stirring at 120 ° C. A composition containing Compound G-7 was obtained.

(Example 18) (Production Method 3)
In a nitrogen atmosphere, 1,150 g of compound G-1 was charged into a reaction vessel, and after 85 g of KBM573 was reacted with stirring, 30 g of β-alanine was further reacted to obtain a composition containing compound D. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 19) (Production method 3)
A composition containing Compound D was obtained by reacting in the same manner as in Example 18 except that β-alanine was changed to 25 g of t-butylamine. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 20) (Production method 3)
A composition containing Compound D was obtained by reacting in the same manner as in Example 19 except that KBM573 was changed to 135 g of Compound X′-1. This compound D has a urethane bond, a substituted urea bond and a Michael addition bond in the molecule.

(Example 21) (Production method 3)
A composition containing Compound D was obtained by reacting in the same manner as in Example 18 except that Compound G-1 was changed to 1,175 g of Compound G-2. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 22) (Production method 3)
A composition containing Compound D was obtained by reacting in the same manner as in Example 19 except that Compound G-1 was changed to 1,175 g of Compound G-2. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 23) (Manufacturing method 3)
A composition containing Compound D was obtained by reacting in the same manner as Example 18 except that Compound G-1 was changed to 2,625 g of Compound G-3 and KBM573 was changed to 75 g of SILQUEST A-Link15. . This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 24) (Production method 3)
A composition containing Compound D was obtained by reacting in the same manner as in Example 23 except that β-alanine was changed to 25 g of t-butylamine. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 25) (Production method 4)
Under a nitrogen atmosphere, 1,150 g of compound G-1 was charged into a reaction vessel, and 265 g of compound X′-1 was reacted with stirring to obtain a composition containing compound D. This compound D has a urethane bond, a substituted urea bond and a Michael addition bond in the molecule.

(Example 26) (Production method 4)
A composition containing Compound D was obtained by reacting in the same manner as in Example 25 except that Compound X′-1 was changed to 180 g of Compound X′-2. This compound D has a urethane bond, a substituted urea bond and a Michael addition bond in the molecule.

(Example 27) (Production method 4)
A composition containing Compound D was obtained by reacting in the same manner as in Example 25 except that Compound X′-1 was changed to 150 g of SILQUEST A-Link15. This compound D has a urethane bond and a substituted urea bond in the molecule.

(Example 28) (Production method 4)
A composition containing Compound D was obtained by reacting in the same manner as in Example 25 except that Compound G-1 was changed to 1,175 g of Compound G-2. This compound D has a urethane bond, a substituted urea bond and a Michael addition bond in the molecule.

(Example 29) (Production method 4)
A composition containing Compound D was obtained by reacting in the same manner as in Example 28 except that Compound X′-1 was changed to 180 g of Compound X′-2. This compound D has a urethane bond, a substituted urea bond and a Michael addition bond in the molecule.

(Example 30) (Production method 4)
A composition containing Compound D was obtained by reacting in the same manner as in Example 25 except that Compound G-1 was changed to a composition containing 2,625 g of Compound G-3. This compound D has a urethane bond, a substituted urea bond and a Michael addition bond in the molecule.

(Example 31) (Production method 4)
A composition containing Compound D was obtained by reacting in the same manner as in Example 30 except that Compound X′-1 was changed to 180 g of Compound X′-2. This compound D has a urethane bond, a substituted urea bond and a Michael addition bond in the molecule.

(Example 32) (Production method 4)
Compound D was reacted in the same manner as in Example 25 except that Compound G-1 was changed to a composition containing 1,400 g of Compound G-4 and Compound X'-1 was changed to 490 g of Compound X'-3. A composition containing was obtained. This compound D has a urethane bond and a Michael addition bond in the molecule.

(Example 33) (Production method 4)
A composition containing Compound D was prepared by reacting in the same manner as in Example 25 except that Compound G-1 was changed to 1,000 g of Compound G-5 and Compound X′-1 was changed to 420 g of Compound X′-3. Obtained. This compound D has a urethane bond and a Michael addition bond in the molecule.

(Example 34) (Production Method 4)
Except for changing Compound G-1 to a composition containing 2500 g of Compound G-6 and Compound X'-1 to 210 g of KBM5103 (trade name, 3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) Was reacted in the same manner as in Example 25 to obtain a composition containing Compound D. This compound D has a Michael addition bond in the molecule.

(Example 35) (Production method 4)
A composition containing Compound D was obtained by reacting in the same manner as in Example 34 except that KBM5103 was changed to 370 g of Compound X′-4. This compound D has a Michael addition bond in the molecule.

(Example 36) (Production method 4)
A composition containing Compound D was prepared by reacting in the same manner as in Example 25 except that Compound G-1 was changed to 2500 g of Compound G-7 and Compound X′-1 was changed to 325 g of Compound X′-3. Obtained. This compound D has a thiourethane bond and a Michael addition bond in the molecule.

(Comparative Example 1)
Under a nitrogen atmosphere, Kanekasairiru MA430 reaction vessel (trade name, manufactured by Kaneka Corporation, modified silicone polymer) of 1,000g was charged, with stirring FTR6100 (trade name thereto, manufactured by Mitsui Chemicals, Inc., _{C 9} petroleum resin ) After heating and melting while gradually adding 1,500 g, Stan No. 3 g of 918 (trade name, manufactured by Sansha Co., Ltd., tin-based catalyst) was blended to obtain a composition.

(Comparative Example 2)
Stan No. A composition was obtained in the same manner as in Comparative Example 1 except that 918 was not blended.

(Comparative Example 3)
A composition was obtained in the same manner as in Comparative Example 1 except that Kanekasilyl MA430 was changed to 1,000 g Epione EP505S (trade name, manufactured by Kaneka Chemical Co., Ltd., hydrolyzable silyl group-containing polyisobutylene polymer).

(Comparative Example 4)
Stan No. A composition was obtained in the same manner as in Comparative Example 3 except that 918 was not blended.

(Comparative Example 5)
Kaneka Silyl MA430 is changed to Bestplast 206 (trade name, manufactured by Degussa Huls, silane-modified amorphous polyalphaolefin) 1,000 g, and FTR6100 is changed to YS Polystar T115 (trade name, manufactured by Yasuhara Chemical Co., terpene phenol resin) 1,500 g. A composition was obtained in the same manner as in Comparative Example 1 except that.

(Comparative Example 6)
Stan No. A composition was obtained in the same manner as in Comparative Example 5 except that 918 was not blended.

(Comparative Example 7)
Under a nitrogen atmosphere, 1,150 g of compound G-1 was charged in a reaction vessel, and 170 g of KBM573 was reacted with stirring. In addition, the Stan No. A composition was obtained by blending 1.5 g of 918.

(Comparative Example 8)
A composition was obtained in the same manner as in Comparative Example 7, except that Compound G-1 was changed to 1,175 g of Compound G-2 and KBM573 was changed to 150 g of SILQUEST A-Link15.

(Comparative Example 9)
A composition was obtained in the same manner as in Comparative Example 7, except that Compound G-1 was changed to 2500 g of Compound G-7 and KBM573 was changed to 158 g of KBM403.

  About each composition obtained by the said Example and comparative example, the melt viscosity stability test, the sclerosis | hardenability test, and the shape retention test were done in the following way, and those results were shown in Table 5.

(Melt viscosity stability test)
Based on 7 of JAI (Adhesive Industry Association Standard), melt viscosity was measured at 120 ° C. using a Brookfield rotary viscometer. The measurement was performed on the initial one, which was cured at 120 ° C. for 2 days without moisture.
The change rate of the melt viscosity value after 2 days with respect to the initial melt viscosity value was calculated by the following formula.
Rate of change (%) = (Difference in melt viscosity after 2 days / initial melt viscosity) × 100
Judgment: ○: Change rate was within ± 30%, x: Change rate was more than ± 30%. Those having a small change in melt viscosity value are judged to be good as a composition for a reactive hot melt adhesive.

(Curing test)
A specimen was prepared based on JIS K 7208 and cured at room temperature for 2 weeks. Then, the test body was left to stand in 100 degreeC oven for 6 hours, and the shape change of the test body was confirmed visually. Judgment was made as follows: ○: No change (cured to the inside), x: Changed (uncured or not cured to the inside). When the specimen shape after 6 hours of standing does not change compared to the initial one, it is judged that the internal curability is good, and it is good as a composition for a reactive hot melt adhesive.

(Shape retention test)
A specimen was prepared based on JIS K 7208 and cured at room temperature for 2 weeks. Then, the test body was left to stand in 100 degreeC oven for 7 days, and the shape change of the test body was confirmed visually. Judgment was made as follows: ○: no change, x: change. It is judged that the test specimen shape after 7 days does not change compared to the initial one is good as a composition for a reactive hot melt adhesive.

  As is clear from the results described in Table 5, the resin compositions according to the examples showed no significant change in melt viscosity and exhibited good internal curability and shape retention. In contrast, the resin composition according to the comparative example has a problem in any of the melt viscosity stability, internal curability, and shape retention tests, and can withstand use as a composition for a reactive hot melt adhesive. I could not.

Claims (7)

  Derived from hydrolyzable silyl group (A), organic group (B) that can act as a hydrolysis catalyst for silyl group (A), urethane bond, thiourethane bond, urea bond, substituted urea bond and Michael addition reaction A reactive hot melt adhesive composition comprising as a component a thermoplastic high molecular weight compound (compound D) having in its molecule one or more types of nitrogen atom-containing bonds (C) selected from chemical bonds.   The compound D according to claim 1 is a molecule of the thermoplastic high molecular weight compound (compound E) having the silyl group (A) according to claim 1 in the molecule and the organic group (B) according to claim 1 as a molecule. A compound obtained by reacting a compound (compound B ′) contained therein and having a nitrogen atom-containing bond (C) according to claim 1 in the molecule. The reactive hot melt adhesive composition described.   The compound D according to claim 1 is a molecule of the thermoplastic high molecular weight compound (compound F) having the organic group (B) according to claim 1 in the molecule and the silyl group (A) according to claim 1. A compound obtained by reacting a compound (compound A ′) contained therein and having a nitrogen atom-containing bond (C) according to claim 1 in the molecule. The reactive hot melt adhesive composition described.   The compound D according to claim 1 is a thermoplastic high molecular weight compound (compound G) having no silyl group (A) and organic group (B) according to claim 1 in its molecule; And a compound having a nitrogen atom-containing bond (C) according to claim 1 in its molecule, obtained by reacting compound A 'according to claim 2 with compound B' according to claim 2. The reactive hot melt adhesive composition according to claim 1.   The compound D according to claim 1 is a compound (compound H) having in its molecule both the compound G according to claim 4 and the silyl group (A) and organic group (B) according to claim 1. The reactive hot melt adhesive composition according to claim 1, which is a compound obtained by reacting with a nitrogen atom-containing bond (C) according to claim 1. Stuff. The silyl group (A) according to any one of claims 1 to 5 is an alkoxysilyl group (X) represented by the following general formula (1). 2. The reactive hot melt adhesive composition according to item 1.
-Si (R ¹ ) _n (R ² ) _3-n (1)
(Wherein, R ¹ represents an alkoxy group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, n represents an integer of 1-3.)   The organic group (B) according to any one of claims 1 to 5 is a basic organic group (Y) containing a tertiary amino group or an acidic organic group (Z) containing a carboxyl group. The reactive hot melt adhesive composition according to any one of claims 1 to 6.