JP2018100322A - Reactive hot-melt adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactive hot-melt adhesive which has high heat resistance, and is excellent in an adhesive force keeping effect at high temperature.SOLUTION: A reactive hot-melt adhesive composition contains (A) an organic polymer having a crosslinkable silicon group and (B) a resin having a crosslinkable silicon group, where (B) the resin having a crosslinkable silicon group is a resin in which a crosslinkable silicon group is bonded to a thermoplastic resin having a hydroxyl group and/or a carboxyl group.SELECTED DRAWING: None

Description

  The present invention relates to a moisture curable reactive hot melt adhesive composition.

A hot melt adhesive is an adhesive that melts and adheres by applying heat at around 100 ° C. Conventionally, a thermoplastic plastic such as ethylene vinyl acetate is generally used as a material for the adhesive, and has an advantage that it is rapidly cured and does not require the use of a solvent.
However, the hot melt adhesive has a problem that its melting and adhesion (solidification) are controlled by heat, so that the heat resistance and the adhesive strength at high temperature are insufficient.

In order to solve this problem of hot melt, a reactive hot melt adhesive has been developed that irreversibly improves the adhesive force by a curing reaction such as crosslinking.
Among them, the development of a reactive hot melt that promotes low toxicity without using an isocyanate compound has been promoted.

  Patent Document 1 discloses a curable composition containing a reactive silicon group-containing oxyalkylene polymer, a tackifier resin, a thixotropic agent, and the like at a specific ratio, and a reactive hot melt adhesive. Yes. The feature of Patent Document 1 is that, by using such a composition, it is possible to provide a moisture-curable reactive hot melt adhesive that has excellent heat-resistant adhesion, has a long pot life during construction, and is less toxic. It is in.

  In Patent Document 2, a moisture-curable reactive hot melt adhesive containing an organic polymer having a reactive silicon group, a resin that is solid at room temperature, a silane coupling agent having a reactive silicon group, and the application method thereof are disclosed. It is disclosed. The feature of Patent Document 2 is such a composition that makes it possible to achieve both heat stability during heating and melting and curability at room temperature after coating, and moisture-curable reactive hot-melt bonding with low toxicity. It is in the point which can provide an agent.

JP 2009-24107 A International Publication 2012/053478

  However, although the hot melt adhesives disclosed in Patent Documents 1 and 2 have improved heat resistance compared to conventional general-purpose hot melt adhesives, the effect of maintaining adhesive strength at high temperatures is not sufficient, and this point No adhesive has yet been obtained that satisfies the heat resistance.

  Then, this invention makes it a subject to provide the reactive hot-melt-adhesive composition which has high heat resistance, and was excellent in especially the adhesive force maintenance effect under high temperature.

  As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by using an organic polymer having a crosslinkable silicon group and a resin having a crosslinkable silicon group in combination. As a result, the present invention has been completed.

That is, according to the present invention, the following reactive hot melt adhesive composition is provided.
(1) (A) an organic polymer having a crosslinkable silicon group, and (B) a resin having a crosslinkable silicon group, wherein the resin (B) having a crosslinkable silicon group is a hydroxyl group and / or A reactive hot melt adhesive composition, which is a resin in which a crosslinkable silicon group is bonded to a thermoplastic resin having a carboxyl group.
(2) The reactive hot melt adhesive composition according to (1), wherein the thermoplastic resin having a hydroxyl group and / or a carboxyl group is an unhydrogenated terpene phenol resin.
(3) (B) The bond amount of the crosslinkable silicon group in the resin having a crosslinkable silicon group is 10 to 90% of the equivalent to the hydroxyl group and / or carboxyl group, as described in (1) or (2) Reactive hot melt adhesive composition.

  According to another aspect of the present invention, an unhydrogenated terpene phenol resin is reacted with a crosslinkable silicon group-containing compound in an amount corresponding to 10% to 90% of the equivalent to the hydroxyl value of the terpene phenol resin. The step of obtaining a resin having a crosslinkable silicon group, the organic polymer having a crosslinkable silicon group, and the resin having a crosslinkable silicon group are put into a stirrer and heated at 80 to 150 ° C. There is provided a method for producing a reactive hot melt adhesive composition, comprising the step of stirring and mixing.

  The reactive hot melt adhesive composition of the present invention is a composition containing (A) an organic polymer having a crosslinkable silicon group and (B) a resin having a crosslinkable silicon group, Since a good crosslinking reaction proceeds and a hardened and highly heat-resistant cured product is obtained, it is excellent in maintaining adhesive strength at high temperatures.

It is the schematic of a heat-resistant creep test.

Hereinafter, the present invention will be described in more detail.
The reactive hot melt adhesive composition of the present invention comprises (A) an organic polymer having a crosslinkable silicon group [(A) component], (B) a resin having a crosslinkable silicon group [(B) component], It is a composition containing these, It is characterized by the above-mentioned. The component (B) is a resin in which a crosslinkable silicon group is bonded to a thermoplastic resin having a hydroxyl group and / or a carboxyl group. Hereinafter, the reactive hot melt adhesive composition of the present invention may be simply referred to as the adhesive composition of the present invention.

  The reactive hot melt adhesive composition of the present invention is a composition used as a moisture curable adhesive, and is an adhesive that is cured and bonded by moisture in the air. That is, the component (A) and the component (B) are softened by heat, and the application to the adhesive surface is facilitated. After application, the crosslinkable silicon groups of the components (A) and (B) are moisture due to moisture in the air By reacting with and curing by crosslinking, the adherend can be firmly bonded.

Hereinafter, each component of the adhesive composition of the present invention will be described.
(A) Component: Organic polymer having a crosslinkable silicon group (A) The crosslinkable silicon group of the organic polymer having a crosslinkable silicon group has a hydroxyl group bonded to a silicon atom or a hydrolyzable group, and has a siloxane bond. It is a group that can be crosslinked by forming. As the crosslinkable silicon group, for example, a group represented by the general formula (1) is preferable.

In formula (1), R ¹ represents an organic group. R ¹ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Among these, R ¹ is particularly preferably a methyl group. R ¹ may have a substituent. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, the plurality of X may be the same or different. a is an integer of 1, 2 or 3.

  Although it does not specifically limit as a hydrolysable group shown by X, For example, an alkoxy group, an acyloxy group, a ketoximate group, an aminooxy group, an alkenyloxy group etc. are mentioned. Among these, an alkoxy group is preferred from the viewpoint of mild hydrolyzability and easy handling. Among alkoxy groups, a group having a small number of carbon atoms has a higher reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and application, a methoxy group or an ethoxy group is preferable.

Specific examples of the crosslinkable silicon group include, for example, trialkoxysilyl groups (—Si (OR ² ) ₃ ) such as trimethoxysilyl group and triethoxysilyl group, dialkylsilyl groups such as methyldimethoxysilyl group and methyldiethoxysilyl group. alkoxysilyl group ^(-SiR 1 ^(OR 2)) and the like. Here, R ² is an alkyl group such as a methyl group or an ethyl group. The trialkoxysilyl group has a higher reactivity than the dialkoxysilyl group, and a fast-curing composition can be prepared. Moreover, since a dialkoxysilyl group is more stable than a trialkoxysilyl group, a stable composition can be prepared.

  (A) The crosslinkable silicon group in a component may be 1 type, or 2 or more types may be mixed. The crosslinkable silicon group may be bonded to either the main chain, the side chain, or both of the organic polymer. In the organic polymer of the component (A), it is preferable that the crosslinkable silicon group is present in an average of 1.0 or more and 5.0 or less in one molecule of the organic polymer, and 1.1 or more and 3.0 More preferably, the number is less than or equal to. When the number of crosslinkable silicon groups contained in one molecule of the organic polymer is less than one, the curability becomes insufficient, and when it exceeds 5.0, the network structure becomes too dense and good mechanical properties. No longer shows.

(A) Examples of the main chain skeleton of the organic polymer having a crosslinkable silicon group include: polyoxyalkylene polymers; hydrocarbon polymers such as polyolefin polymers and hydrogenated polyolefin polymers; Polymers: Vinyl polymers such as (meth) acrylic acid ester polymers; graft polymers obtained by further polymerizing vinyl monomers with these organic polymers, and the like.
Further, these skeletons may be contained alone in (A) the organic polymer having a crosslinkable silicon group, or two or more kinds may be contained in blocks or randomly.

  Saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers have a relatively low glass transition temperature, and the resulting cured product This is preferable because the brittleness of the resin is well improved. Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because of their high moisture permeability and excellent deep-part curability.

A polymer having a main chain skeleton of an oxyalkylene polymer and having a crosslinkable silicon group at the terminal is a polymer having a repeating unit represented by the general formula (2).



[In formula (2), R ³ is a linear or branched alkylene group having a carbon number of 1 to 14, preferably a linear or branched alkylene group having 2 to 4 carbon atoms. ]

Specific examples of the repeating unit represented by the general formula (2) include —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH ₂ CH ₂ CH ₂ O—, and the like. . The main chain skeleton of the polyoxyalkylene polymer having a crosslinkable silicon group may consist of only one type of repeating unit or two or more types of repeating units. In particular, a main chain skeleton composed of a polymer mainly composed of oxypropylene is preferable.

  The number average molecular weight of the polyoxyalkylene polymer having a crosslinkable silicon group is preferably 15,000 or more, more preferably 18,000 or more, and further preferably 20,000 or more. Moreover, 50,000 or less is preferable and 40,000 or less is more preferable. In addition, a number average molecular weight is a polystyrene conversion molecular weight by gel permeation chromatography. If the number average molecular weight is less than 15,000, the tensile modulus and elongation at break may not be sufficient. If it exceeds 50,000, the viscosity of the composition may increase and workability may be reduced.

  If the content of the crosslinkable silicon group in the polyoxyalkylene polymer is controlled to an appropriate ratio, the crosslink density in the cured product will decrease, resulting in a more flexible cured product, with reduced modulus properties and elongation at break properties. Becomes larger. In the polyoxyalkylene polymer, the number of crosslinkable silicon groups is preferably 1.2 or more and 2.8 or less on average in one molecule of the polymer, and is 1.3 or more and 2.6 or less. More preferably, it is more preferably 1.4 or more and 2.4 or less.

  The polyoxyalkylene polymer having a crosslinkable silicon group may be linear or branched. From the viewpoint of reducing the tensile modulus, the polyoxyalkylene polymer having a crosslinkable silicon group is preferably a linear polymer. The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer having a crosslinkable silicon group is preferably 2 or less, particularly 1.6 or less.

  Examples of the synthesis method of the polyoxyalkylene polymer include, but are not limited to, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a double metal cyanide complex catalyst, and the like. According to the polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene polymer having a high molecular weight and a narrow molecular weight distribution with Mw / Mn of 1.6 or less can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer may contain other structural units such as a urethane bond. Examples of the urethane bond include structural units obtained from a reaction between an aromatic polyisocyanate such as toluene diisocyanate; an aliphatic polyisocyanate such as isophorone diisocyanate and a polyoxyalkylene polymer having a hydroxyl group. .

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be performed on a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group, or an isocyanate group in the molecule. This is possible by reacting a functional group having reactivity and a compound having a crosslinkable silicon group (hereinafter referred to as a polymer reaction method).

  As an example of a polymer reaction method, hydrosilylation or mercaptosis is caused by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer. The method of obtaining the polyoxyalkylene type polymer which has can be mentioned. An unsaturated group-containing polyoxyalkylene polymer can be obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group. it can.

  Other examples of the polymer reaction method include a method in which a polyoxyalkylene polymer having a hydroxyl group at a terminal is reacted with a compound having an isocyanate group and a crosslinkable silicon group, or a polymer having an isocyanate group at a terminal. Examples thereof include a method of reacting an oxyalkylene polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group, and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  The polyoxyalkylene polymer having a crosslinkable silicon group may be one kind or a combination of two or more kinds.

  Various monomers can be used as a monomer for producing a (meth) acrylic acid ester polymer, which is one of the main skeletons of the organic polymer having a crosslinkable silicon group of the present invention. For example, (meth) acrylic acid monomers; (meth) acrylic acid alkyl ester monomers such as n-butyl (meth) acrylate and stearyl (meth) acrylate; alicyclic (meth) acrylic acid monomers; aromatic Group (meth) acrylic acid ester monomers; (meth) acrylic acid ester monomers such as 2-methoxyethyl (meth) acrylate; silyl group-containing (meth) acrylic acids such as γ- (methacryloyloxypropyl) trimethoxysilane Examples include ester monomers.

  In the (meth) acrylic acid ester polymer, a vinyl monomer can be copolymerized with the (meth) acrylic acid ester monomer. Examples of vinyl monomers include styrene, maleic anhydride, vinyl acetate and the like. In addition to these, acrylic acid may be contained as monomer units (hereinafter also referred to as other monomer units).

  One of these monomers may be homopolymerized, or a plurality of these monomers may be copolymerized. From the viewpoint of physical properties such as the adhesion performance of the organic polymer, a copolymer of a monomer composition containing a plurality of types of monomers is preferred. For example, a monomer composition containing one or two or more (meth) acrylic acid alkyl ester monomers, and (meth) acrylic acid monomers and / or other vinyl monomers as necessary is polymerized. An acrylic ester copolymer is more preferable. Furthermore, the number of silicon groups in the (meth) acrylic acid ester polymer can be controlled by using a (meth) acrylic acid ester monomer having a crosslinkable silicon group in combination. From the viewpoint of adhesiveness, a copolymer of a monomer composition containing a methacrylic acid ester monomer as an essential component is particularly preferable. Moreover, when appealing low viscosity and a softness | flexibility provision, it is preferable to use an acrylate ester monomer suitably. In addition, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  As a method for producing the (meth) acrylic acid ester polymer, for example, a radical polymerization method using a radical polymerization reaction can be used. The radical polymerization method includes a radical polymerization method (free radical polymerization method) in which a predetermined monomer is copolymerized using a polymerization initiator, or a controlled radical weight capable of introducing a crosslinkable silicon group at a controlled position such as a terminal. Lawful. However, a polymer obtained by a free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a large molecular weight distribution value of 2 or more and a high viscosity. Therefore, in the case of obtaining a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable silicon group at the molecular chain terminal at a high ratio, It is preferable to use a controlled radical polymerization method.

  Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group. A living radical polymerization method such as an atom transfer radical polymerization method (ATRP) is preferably employed. In addition, as a reaction for synthesizing a polymer whose main chain skeleton is a (meth) acrylic acid ester polymer and a part of which is a telechelic polymer (hereinafter referred to as “pseudo telechelic polymer”), crosslinkability Examples include a reaction using a thiol compound having a silicon group, a reaction using a thiol compound having a crosslinkable silicon group, and a metallocene compound.

  The organic polymer having a crosslinkable silicon group exemplified above may be one kind or a combination of two or more kinds. Specifically, a group consisting of a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. The organic polymer which blended 2 or more types selected from can be used. In particular, an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group has excellent characteristics.

There are various methods for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. For example, from a structural unit derived from a (meth) acrylic acid ester monomer having a crosslinkable silicon group and the structural unit of the main skeleton being substantially represented by the general formula (3) and the general formula (4) And a method of blending a polyoxyalkylene polymer having a crosslinkable silicon group with the copolymer.

[In Formula (3), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an alkyl group having 1 to 5 carbon atoms. Preferably, an alkyl group having 1 to 2 carbon atoms is used. Incidentally, R ⁵ alone may be, or two or more may be mixed. ]

[In Formula (4), R ⁴ is the same as Formula (3), and R ⁶ represents an alkyl group having 6 or more carbon atoms. Preferably, long-chain alkyl groups having 8 to 20 carbon atoms such as 2-ethylhexyl group and stearyl group are exemplified. Incidentally, R ⁶ alone may be, or two or more may be mixed. ]

  Here, “substantially” means that the total of the structural units of the formula (3) and the formula (4) present in the copolymer exceeds 50% by mass. The total of the structural units of formula (3) and formula (4) is preferably 70% by mass or more. The abundance ratio of the structural unit of the formula (3) to the structural unit of the formula (4) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40 in terms of mass ratio.

  The number average molecular weight of the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is preferably 600 or more and 10,000 or less, more preferably 1,000 or more and 5,000 or less, and 1,000 or more and 4,500 or less. Is more preferable. By setting the number average molecular weight within this range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group is improved. The (meth) acrylic acid ester-based polymer having a crosslinkable silicon group may be one kind or a combination of two or more kinds. The compounding ratio of the polyoxyalkylene polymer having a crosslinkable silicon group and the (meth) acrylic acid ester polymer having a crosslinkable silicon group is not particularly limited, but the (meth) acrylic acid ester polymer and It is preferable that the (meth) acrylic acid ester polymer is in the range of 20 parts by mass or more and 70 parts by mass or less, and 30 parts by mass or more and 60 parts by mass with respect to 100 parts by mass in total with the polyoxyalkylene polymer. The following range is more preferable. When the amount of the (meth) acrylic acid ester polymer is more than 70 parts by mass, the viscosity becomes high and workability may be deteriorated. Moreover, when it is less than 20 mass parts, initial adhesiveness may be insufficient.

In the present invention, an organic polymer obtained by blending a saturated hydrocarbon polymer having a crosslinkable silicon group and a (meth) acrylic acid ester copolymer having a crosslinkable silicon group can also be used.
In addition, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group, in the presence of an organic polymer having a crosslinkable silicon group, A method of polymerizing a (meth) acrylic acid ester monomer can be used.

Component (B): Resin having a crosslinkable silicon group The component (B) is a resin in which a crosslinkable silicon group is introduced into a hydroxyl group and / or carboxyl group-containing thermoplastic resin.
The hydroxyl group and / or carboxyl group-containing thermoplastic resin [hereinafter also referred to as component (B) thermoplastic resin. ] May be any of natural resins, modified products thereof, and synthetic resins, such as terpene phenol resins and hydrogenated products thereof, hydroxyl group and / or carboxyl group-containing rosins and derivatives thereof, xylene resins, phenols, etc. And xylene resin modified with the above.

  In particular, natural resins and modified products thereof are preferable in terms of good compatibility with the component (A). Examples include terpene phenol resins and hydrogenated products thereof, hydroxyl group and / or carboxyl group-containing rosins and derivatives thereof. Can do. When a natural resin or a modified product thereof is used, in the terpene phenol resin or hydrogenated product thereof, a crosslinkable silicon group is introduced by reacting a hydroxyl group with a crosslinkable silicon group-containing compound having an isocyanate group or an epoxy group. In the case of rosin having a hydroxyl group and / or carboxyl group, a crosslinkable silicon group is introduced by reacting the hydroxyl group and / or carboxyl group with a crosslinkable silicon group-containing compound having an isocyanate group or an epoxy group. .

  As the component (B) thermoplastic resin for introducing a crosslinkable silicon group, it is particularly preferable to use an unhydrogenated terpene phenol resin. This is because a composition having good compatibility with other components and particularly excellent adhesion performance can be obtained.

  For example, when a terpene phenol resin is used as the thermoplastic resin for component (B), the terpene phenol resin preferably has a hydroxyl value of 30 to 250 KOH mg / g, more preferably 50 to 200 KOH mg / g, Particularly preferred is ~ 150 KOHmg / g. Specifically, YS polystar T, YS polyster S, YS polyster G, YS polyster N, YS polystar K, etc. manufactured by Yasuhara Chemical Co., Ltd. may be mentioned.

  (B) The crosslinkable silicon group introduced into the component thermoplastic resin is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. It may be the same as the crosslinkable silicon group of the component.

As above-mentioned, a crosslinkable silicon group is introduce | transduced by reaction with the hydroxyl group and / or carboxyl group of the thermoplastic resin for (B) components. Therefore, the amount of the crosslinkable silicon group in the component (B) is preferably 10 to 90%, and preferably 30 to 70% of the equivalent to the hydroxyl group and / or carboxyl group of the thermoplastic resin for the component (B). It is particularly preferred. That is, the crosslinkable silicon group-containing compound in an amount corresponding to 10 to 90%, preferably 30 to 70% of the equivalent of the hydroxyl value of the thermoplastic resin for component (B) is reacted with the thermoplastic resin for component (B). It is preferable to make it. Moreover, what is necessary is just to set it as the desired crosslinkable silicon group introduction | transduction rate within the said range in consideration of the magnitude of the hydroxyl value of the thermoplastic resin for (B) components.
If the introduction rate of the crosslinkable silicon group is too low, the heat resistance may be insufficient, and if it is too high, the compatibility with the component (A) may be deteriorated.

Specific examples of the method for introducing the crosslinkable silicon group into the thermoplastic resin for component (B) include the following methods.
(B) The thermoplastic resin for component and the crosslinkable silicon group-containing compound having an isocyanate group or an epoxy group are added to a mixing vessel and reacted while stirring. Furthermore, in order to accelerate the reaction, heating to about 70 ° C. to 100 ° C. or a catalyst such as tin may be added.

  Specific examples of the crosslinkable silicon group-containing compound having an isocyanate group or an epoxy group include isocyanate silane and epoxy silane. As these silane compounds, commercially available products may be used. As isocyanate silane, KBE-9007 (3-isocyanatopropyltriethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.), and epoxy silane, KBM-403 (3-glycidide). And xylpropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.).

  Moreover, you may use what made the isocyanate compound react with the secondary aminosilane compound. Further, a compound obtained by Michael addition of a compound having an amino group and a compound having a (meth) acryloyl group, wherein a Michael adduct having a crosslinkable silicon group is reacted with an isocyanate compound may be used. good.

  A commercially available product may be used as the secondary aminosilane compound, and KBM-573 (N-phenyl-3-aminopropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.) can be exemplified.

  The following are mentioned as an example of the manufacturing method of the Michael adduct which has a crosslinkable silicon group.

(A) A compound having a crosslinkable silicon group and (meth) acryloyl group is reacted with a compound having no crosslinkable silicon group and having an amino group.
(B) A compound having no (crosslinkable silicon group) and having a (meth) acryloyl group is reacted with a compound having a crosslinkable silicon group and an amino group.
(C) A compound having a crosslinkable silicon group and a (meth) acryloyl group is reacted with a compound having a crosslinkable silicon group and an amino group.
Hereinafter, a compound having a crosslinkable silicon group and a (meth) acryloyl group is also referred to as (meth) acryloylsilane, and a compound having a crosslinkable silicon group and an amino group is also referred to as aminosilane.

  Examples of (meth) acryloylsilane include (meth) acryloxysilane compounds such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane. These may be used alone or in combination of two or more.

  Examples of aminosilane include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane Other special aminosilanes manufactured by Shin-Etsu Chemical Co., Ltd., trade names: KBM6063, X-12-896, KBM576, X-12-565, X-12-580, X-12-806, X-12-666 X-12-5263, KBM6123, X-12-577, -12-575, X-12-563B, aminosilane compounds such as X-12-562 and the like. Of these, compounds having a primary amino group are preferred. These may be used alone or in combination of two or more.

  Examples of the compound having no crosslinkable silicon group and having an amino group include ethylamine, allylamine, isopropylamine, 2-ethylhexylamine, 2-ethylhexyloxylpropylamine, 3-ethoxypropylamine, t-butylamine, sec-butylamine, Mono primary amine compounds such as propylamine, 3-methoxypropylamine, stearylamine, 2-phenylethylamine, diisopropylamine, diethylamine, diisobutylamine, di (2-ethylhexyl) amine, 2-pyrrolidone, various imidazole compounds, pyrrolidine, Secondary amine compounds such as piperidine and 1-benzylpiperazine, primary and secondary such as 3-diethylaminopropylamine, dibutylaminopropylamine and 3- (dimethylamino) propylamine Or the like can be used a compound having an amino group. Of these, compounds having a primary amino group are preferred. These may be used alone or in combination of two or more.

  Examples of the compound having no (meth) acryloyl group without having a crosslinkable silicon group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-ethoxy Suitable examples include ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, n-stearyl (meth) acrylate, and (meth) acrylic acid esters such as ethyl 2-cyanoacrylate. These may be used alone or in combination of two or more.

  The reaction conditions of the compound having the (meth) acryloyl group and the compound having an amino group are not particularly limited, but both of them are -20 ° C to 120 ° C, regardless of the presence or absence of a crosslinkable silicon group, and 0. It is preferable to carry out the mixing reaction for about 5 to 1000 hours. Both reactions may be performed at room temperature to 120 ° C., but may be cooled as necessary. The reaction may be performed in the presence of a medium such as an organic solvent, and there is no problem if it is performed for more than 1000 hours. The compounding ratio of the amine and the (meth) acryloyl compound at the time of the reaction was γ active hydrogens in 1 mol of the amine and δ functional groups that react with the amino groups in 1 mol of the (meth) acryloyl compound. In this case, it is preferable that (meth) acryloylsilane is in a range of 1 / δ to γ mol with respect to 1 mol of aminosilane.

  The isocyanate compound to be reacted with the secondary aminosilane compound or the Michael adduct having a crosslinkable silicon group is a compound having two or more isocyanate groups in one molecule, and generally has an isocyanate group in one molecule. Compounds containing 2 to 5 are preferred. The isocyanate group is preferably an isocyanate group bonded to an alkylene group, a cycloalkylene group, a phenylene group or the like.

  Examples of the isocyanate compound include tolylene diisocyanate (including various mixtures of isomers), diphenylmethane diisocyanate (including various mixtures of isomers), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4. -Aromatic diisocyanates such as phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, 1,4- Cyclohexyl diisocyanate, 1-methyl-2,4-diisocyanato-cyclohexane, 2,4,4-trimethyl-1,6-diisocyanato-hexane Diisocyanates such as aliphatic diisocyanates and alicyclic diisocyanates, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, tris (4-phenylisocyanato) thiophosphate, triisocyanates such as aromatic triisocyanate, the isocyanate Urethanization-modified products, isocyanurate-modified products, carbodiimidization-modified products, burette-modified products, crude tolylene isocyanate, crude diphenylmethane diisocyanate, polymethylene isocyanate such as polymethylene / polyphenyl isocyanate, and the like.

  As a blending ratio of the components (A) and (B) in the reactive hot melt adhesive composition, the component (B) is preferably 10 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the component (A). 30 parts by mass or more and 250 parts by mass or less is more preferable. If the amount is less than 10 parts by mass, initial adhesiveness may not be exhibited. Moreover, when there are more (B) components than 500 mass parts, the physical property after hardening may become weak.

  The reactive hot melt adhesive composition of the present invention may optionally contain other components other than the components (A) and (B) as long as the object of the present invention is not impaired. The other components include curing catalysts, fillers, adhesion promoters, diluents, plasticizers, moisture absorbers, physical property modifiers that improve tensile properties, reinforcing agents, colorants, flame retardants, sagging inhibitors. , Antioxidants, anti-aging agents, ultraviolet absorbers, solvents, fragrances, dyes, conductivity-imparting agents, thermal conductivity-imparting agents, and the like.

  Specific examples of the curing catalyst include alkyl titanates, organosilicon titanates, bismuth tris-2-ethylhexoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin maleate, Examples include metal salts of carboxylic acids such as dioctyltin diacetate, tin octylate, tin naphthenate, etc .: amine salts such as dibutylamine-2-ethylhexoate, and other acidic and basic catalysts. . Of these, organotin compounds are preferred. The curing catalyst acts as a curing catalyst for the component (A). When a curing catalyst is used, it is preferably used in a range of usually 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of component (A).

  Examples of fillers include reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, hardened titanium, bentonite, organic Fillers such as bentonite, ferric oxide, zinc oxide and activated zinc white; hollow fillers such as glass balloons and shirasu balloons; fibrous fillers such as asbestos, glass fibers and filaments can be used.

  Examples of the adhesion imparting agent include various silane coupling agents. Specific examples of the silane coupling agent include amino group-containing silanes such as N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane. An epoxy group-containing silane such as γ-glycidoxypropyltrimethoxysilane; a vinyl-type unsaturated group-containing silane such as vinyltrimethoxysilane; an isocyanate group-containing silane such as γ-isocyanatopropyltrimethoxysilane; These silane coupling agents may be used alone or in combination of two or more.

Next, the manufacturing method of one Embodiment of the reactive hot-melt-adhesive composition of this invention is demonstrated.
Components (A) and (B), and other components as desired, are added to an agitating (mixing) device in any order, and each compounding component is heated to 80 to 150 ° C., more preferably about 100 to 120 ° C. It can be produced by stirring and mixing until uniform.

It continues and demonstrates the usage method (adhesion method) of the reactive hot-melt-adhesive composition of this invention.
The reactive hot melt adhesive composition of the present invention can be used in the same manner as known reactive hot melt adhesives, and the composition is heated to 70 to 140 ° C. and applied to an adherend. It can adhere | attach by bonding an adhesion surface. The composition may be applied to only one of the adhesive surfaces, or may be applied to both adhesive surfaces.

  The adhesive composition of the present invention is used as a reactive hot melt adhesive for various uses and for bonding substrates. The use is not particularly limited, and examples thereof include architecture, automobiles, electric / electronic parts and products, and textile / leather / clothing applications.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

The number average molecular weight was measured under the following conditions by gel permeation chromatography (GPC) unless otherwise specified. The maximum frequency molecular weight measured by GPC under the following measurement conditions and converted to standard polystyrene is referred to as “number average molecular weight”.
・ Analyzer: Alliance (manufactured by Waters), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Millenium data processor (manufactured by Waters)
Column: PlgelGUARD + 5 μmMixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by PolymerLab)
-Flow rate: 1 mL / min-Converted polymer: polystyrene-Measurement temperature: 40 ° C
・ Solvent for GPC measurement: THF

(Synthesis Example 1) Synthesis of (meth) acrylic organic polymer A1 having a trimethoxysilyl group In a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 40.00 g of ethyl acetate, methyl 70.00 g of methacrylate, 30.00 g of 2-ethylhexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.00 g of 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), and metal catalyst 0.10 g of titanocene dicylide was charged and the contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. Next, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added all at once to the flask with stirring. After adding 4.30 g of 3-mercaptopropyltrimethoxysilane, heating and cooling were performed for 4 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. Further, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added to the flask over 5 minutes with stirring. After the additional addition of 4.30 g of 3-mercaptopropyltrimethoxysilane, the reaction was carried out for 4 hours while further cooling and heating so that the temperature of the contents in the stirring flask could be maintained at 90 ° C. . After a total of 8 hours and 5 minutes of reaction, the temperature of the reaction product was returned to room temperature, 20.00 g of a benzoquinone solution (95% THF solution) was added to the reaction product to terminate the polymerization, and a trimethoxysilyl group (meta ) Acrylic organic polymer A1 was obtained. The peak top molecular weight was 4000, and the molecular weight distribution was 2.4. The number of trimethoxysilyl groups contained by H1-NMR measurement was 2.00 per molecule.

(Synthesis Example 2) Synthesis of Resin B1 Having Crosslinkable Silicon Group A 500 ml separable flask contains 100 g of YS Polystar G150 (trade name) (terpene phenol resin, manufactured by Yashara Chemical Co., Ltd., hydroxyl value: 130 mg / KOHg). 200 g of 50% ethyl acetate solution of the resin, KBE-9007 (trade name) (3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 28.7 g (50% of the equivalent of the hydroxyl value of YS Polystar G150) And Neostan (registered trademark) U-100 (dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) 0.13 g was added, and the mixture was stirred and reacted at 70 ° C. for 8 hours to obtain an ethyl acetate solution of B1. .
As a result of IR spectrum measurement of B1, it was confirmed that the isocyanate group (—NCO) absorption peak disappeared and a new absorption peak due to —C═O of the urethane bond was generated.

(Synthesis Example 3) Synthesis of Resin B2 Having Crosslinkable Silicon Group To a 500 ml separable flask, 24.2 g of isobornyl acrylate and 20.8 g of KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the temperature was 50 ° C. And stirred for 24 hours. Next, 25.8 g of isophorone diisocyanate was added and reacted at 23 ° C. for 3 hours. Thereafter, 200 g of a 50% ethyl acetate solution of YS Polystar G150 and 0.18 g of Neostann U-100 were added and mixed and stirred at 70 ° C. for 8 hours to obtain an ethyl acetate solution of B2. The amount of crosslinkable silicon group introduced was 50% of the equivalent of the hydroxyl value of YS Polystar G150.
As a result of IR spectrum measurement of B2, it was confirmed that the absorption peak of the isocyanate group (—NCO) disappeared and a new absorption peak due to —C═O of the urethane bond was generated.

Example 1
After the components (A), (B), and the antioxidant were mixed in the pressure-blending vessel with a stirrer at a blending ratio shown in Table 1, the ethyl acetate was distilled off by stirring and mixing at 100 ° C. under reduced pressure. A curing catalyst and an adhesion-imparting agent were added, and the composition 1 was obtained by stirring and mixing again under reduced pressure at 100 ° C. for 5 minutes. In addition, the quantity of B1 of Table 1 is an quantity which does not contain ethyl acetate (B2 of the below-mentioned Example 2 is also the same).

(Performance evaluation of composition 1; heat-resistant creep test)
The composition 1 heated to 110 ° C. is applied to a canvas (width 25 mm × length 80 mm) at a thickness of 100 μm, an aluminum plate (width 25 mm × length 75 mm) is bonded, and a 2 kg roller is reciprocated twice. After tightening, the specimen 1 was obtained by allowing to stand for 1 week in an environment of 23 ° C. and humidity 50% RH. The obtained test body 1 is fixed horizontally, and one end of the canvas is peeled off from the aluminum plate by a length of 25 mm so that the bonded portion between the canvas and the aluminum plate is 25 mm wide × 50 mm long. The weight (500 g) was hung so that a load was applied in the direction of 90 degrees. The state at the start of the test is shown in FIG.
It was allowed to stand at 70 ° C. and 80 ° C. for 24 hours, and the distance during which the canvas peeled from the aluminum plate (peeling distance; mm) was measured. The peeled distance was measured using the initial state at the start of the test as a reference (0 mm). The results are shown in Table 1.

(Example 2, Comparative Examples 1-3)
Each compounding substance was added at the compounding ratio shown in Table 1, and compositions 2 to 5 were produced in the same manner as in Example 1.

(Performance evaluation of compositions 2-5; heat-resistant creep test)
Specimens 2 to 5 using compositions 2 to 5 were prepared in the same manner as in Example 1, and a heat-resistant creep test was conducted in the same manner as Specimen 1. The results are shown in Table 1.

Comparative Example 2 is a composition based on the curable composition disclosed in Patent Document 1, and Comparative Example 3 is a composition based on the curable composition disclosed in Patent Document 2.
As is clear from Table 1, the reactive hot melt adhesive compositions of the examples according to the present invention can be completely peeled off the aluminum plate even when exposed to high temperatures of 70 ° C. and 80 ° C. for 24 hours. Without maintaining a strong adhesive force. On the other hand, the composition of each comparative example resulted in the canvas completely peeling from the aluminum plate due to the exposure.
That is, it was proved that the compositions of the examples exhibited markedly superior heat resistance creep test evaluations as compared with the compositions of the comparative examples, and exhibited extremely excellent heat resistance.

1 Canvas 2 Aluminum plate 3 Weight

Claims (4)

(A) an organic polymer having a crosslinkable silicon group;
(B) a resin having a crosslinkable silicon group,
The resin having a crosslinkable silicon group (B) is a resin in which a crosslinkable silicon group is bonded to a thermoplastic resin having a hydroxyl group and / or a carboxyl group.
Reactive hot melt adhesive composition. The thermoplastic resin having a hydroxyl group and / or a carboxyl group is an unhydrogenated terpene phenol resin.
The reactive hot melt adhesive composition according to claim 1. The bond amount of the crosslinkable silicon group in the resin having the (B) crosslinkable silicon group is 10 to 90% of the equivalent to the hydroxyl group and / or carboxyl group.
The reactive hot melt adhesive composition according to claim 1 or 2. A step of reacting an unhydrogenated terpene phenol resin with a crosslinkable silicon group-containing compound in an amount corresponding to 10% to 90% of the equivalent of the hydroxyl value of the terpene phenol resin to obtain a resin having a crosslinkable silicon group And a step of putting the organic polymer having a crosslinkable silicon group and the resin having the crosslinkable silicon group into a stirrer and stirring and mixing while heating at 80 to 150 ° C.
A method for producing a reactive hot melt adhesive composition.