WO2021033628A1

WO2021033628A1 - Composition

Info

Publication number: WO2021033628A1
Application number: PCT/JP2020/030825
Authority: WO
Inventors: 弘基宇野; 貴子谷川; 山下　幸彦
Original assignee: デンカ株式会社
Priority date: 2019-08-22
Filing date: 2020-08-13
Publication date: 2021-02-25
Also published as: JPWO2021033628A1; JP7022870B2

Abstract

The present invention ensures a sufficient working life, while having adhesiveness to a poorly adhesive adherend. A composition which contains the components (1) to (4) described below. (1) a (meth)acrylate (2) an alkylborane-amine complex (3) a compound which is addition reactive with an amine (4) a phosphate compound containing a metal

Description

Composition

The present invention relates to a composition.

Polyolefins such as polyethylene and polypropylene are used in a wide range of fields as materials for automobile parts, electrical parts, building materials, food packaging films, and the like. Since polyolefin is a non-polar material, it is a difficult-to-adhere body (also referred to as “hard-to-bond body”) that is difficult to adhere.

In general, it is known that adhesion of dissimilar materials is difficult because it is necessary to balance the adhesiveness of the adhesive to each material. When dissimilar materials are bonded with an adhesive and force is applied, the adhesive is destroyed from the weakest adhesive strength, so the adhesive must have appropriate adhesiveness to both materials. However, since metals containing iron, aluminum, zinc, etc. have high surface polarity, it is difficult to exhibit high adhesiveness with an adhesive for non-polar materials such as polyolefin.

The two-component main agent type (two-agent type) acrylic adhesive has the characteristics that it cures in a short time at room temperature, the effect of mixing ratio deviation is small, and the balance between adhesion and peeling is excellent. It is used in a wide range of fields as an adhesive.

However, the conventional two-component main agent type acrylic adhesive has low adhesiveness to both polyolefins and metals, like other adhesives.

When adhering to these difficult-to-attach bodies, surface treatment such as flame treatment, itro treatment, corona discharge, plasma treatment, oxidation with ozone or acid, and sputter etching is often required. When adhering to these difficult-to-attach bodies, the surface of the difficult-to-attach body may be coated with a primer, but in many cases, the above surface treatment is required in the end for the primer adhesion, and the surface In many cases, sufficient adhesiveness cannot be obtained even after treatment.

It was very difficult to enable heterogeneous adhesion with a two-component main agent type acrylic adhesive. Further, since the conventional two-component main agent type acrylic adhesive cures in a short time, there is a problem that a sufficient pot life cannot be obtained.

Patent Documents 1 and 2 disclose an adhesive that starts a polymerization reaction and cures by deprotecting organic borane with an isocyanate compound. However, the isocyanate compound has extremely high reactivity, and actually has a problem that a sufficient usable time of the adhesive cannot be secured.

In Patent Document 3, one kind containing an organic boron compound capable of forming a free radical generation species and a nitrile oxide of dihydrocarbyl hydroxylamine or alicyclic hydroxylamine or dihydrocarbylamine or alicyclic hydroxylamine in the first portion. Disclosed is a dipartic polymerizable composition comprising one or more compounds, and one or more compounds capable of free radical polymerization in the second portion. However, when exposed to the temperature at which the polymerization starts, the reaction rate that has started cannot be effectively controlled, and there is a problem that a sufficient pot life cannot be secured.

Patent Document 4 discloses a curable composition containing a curable acrylate or methacrylate component, an organoborane initiator component, a vinyl ether component, and an activator for the organoborane component. However, the method of Patent Document 4 cannot solve the problem that the curing rate due to the vinyl ether component becomes too high and the gelation time (potential time) becomes short.

JP-A-2017-149789 JP-A-2010-280891 Japanese Patent Publication No. 2008-502742 Special Table 2016-513744

In the prior art as disclosed in the above-mentioned Patent Documents 1 to 4, there remains a problem that the adhesiveness to the difficult-to-attached body is inferior or the pot life cannot be sufficiently secured. Therefore, there is a long-awaited method that can solve these problems together.

The present invention has been made in view of the above problems. That is, the present invention can provide the following.

[1]
A composition containing the following components (1) to (4).
(1) (Meta) acrylate (2) Alkylborane-amine complex (3) Compound that undergoes an addition reaction with amine (4) Phosphate compound containing a metal

[2]
(4) The composition according to [1], wherein the component is a compound having a (meth) acryloyl group or a polymer thereof.

[3]
(4) The composition according to [1] or [2], wherein the metal contained in the component is one or more selected from alkali metals and alkaline earth metals.

[Four]
(4) The composition according to [3], wherein the metal contained in the component is lithium, sodium, or both.

[Five]
(4) The composition according to any one of [1] to [4], wherein the ratio of the amount of substance of the metal to the P-OH group in the component is 0.1 to 0.85 molar equivalent.

[6]
(4) The item according to any one of [1] to [5], wherein the amount of the component used is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the components (1) to (4). Composition.

[7]
(4) The composition according to any one of [1] to [6], wherein the component is a monomer.

[8]
(4) The composition according to any one of [1] to [6], wherein the component is a polymer.

[9]
(1) The composition according to any one of [1] to [8], wherein the component contains any one or more of the following.
(1-1) (Meta) acrylate having a cyclic ether skeleton (1-2) (Meta) acrylate having an aromatic ring (1-3) Di (meth) acrylate having a bisphenol A skeleton

[Ten]
(2) The component is one or more selected from the group consisting of triethylborane-1,3-diaminopropane complex, triethylborane-diethylenetriamine complex, and tributylborane-3-methoxy-1-propylamine complex. The composition according to any one of [1] to [9].

[11]
(2) The item according to any one of [1] to [10], wherein the content of the component is 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of the components (1) to (4). Composition.

[12]
(3) The composition according to any one of claims [1] to [11], wherein the component contains an acid anhydride.

[13]
(3) The composition according to [12], wherein the component contains an acid anhydride monomer in a polymer compound having a number average molecular weight of 10,000 or more.

[14]
The composition according to [13], wherein 5 to 25% by mass of the monomer units in the polymer compound component is an acid anhydride monomer.

[15]
The composition according to any one of [12] to [14], wherein the acid anhydride is a copolymer of a (meth) acrylic acid ester, an aromatic vinyl, and an acid anhydride.

[16]
Of the monomer units in the copolymer, acid anhydride is 10 to 25% by mass, (meth) acrylic acid ester is 5 to 35% by mass, and aromatic vinyl is 50 to 75% by mass [15]. The composition according to.

[17]
(3) The composition according to any one of [1] to [16], wherein the amount of the component used is 1 to 30 parts by mass with respect to a total of 100 parts by mass of the components (1) to (4). ..

[18]
A two-component composition having a first agent and a second agent, wherein the first agent contains at least the component (2) and the second agent contains at least (1), (3), and (4). The composition according to any one of [1] to [17], which contains an ingredient.

[19]
A curable resin composition containing the composition according to any one of [1] to [18].

[20]
An adhesive composition containing the composition according to any one of [1] to [18].

[twenty one]
A cured product of the composition according to any one of [1] to [18].

[twenty two]
A method of adhering an adherend using the adhesive composition according to [20].

[twenty three]
The method according to [22], wherein the adherend is one or more of the group consisting of polyolefins, cycloolefins, polystyrenes, fiber reinforced plastics, and metals.

[twenty four]
A bonded body bonded by the curable resin composition according to [19] or the adhesive composition according to [20].

The composition according to the embodiment of the present invention has an effect that it has adhesiveness to a difficult-to-adhere body such as polyolefin and has a sufficiently long pot life (open time).

In the present specification, unless otherwise specified, the numerical range shall include the upper limit value and the lower limit value. When the composition of the present invention is used separately for the first agent and the second agent, the "usage amount" or "content" of each component in the composition means the component in the first agent and the second agent. The total amount of.

The (meth) acrylate, which is the component (1) used in the present embodiment, is a compound having a (meth) acryloyl group. The (meth) acrylate is preferably a monomer. The (meth) acryloyl group means an "acryloyl group" or a "methacryloyl group". The notation "(meth) acrylate" means "acrylate" or "methacrylate".

(1) The component has a function of dissolving other components of the present composition. Since the component (1) is preferably compatible with various components and has a high affinity for an adherend such as an olefin, a structure having a cyclic structure is preferable.

In a preferred embodiment, the (1) (meth) acrylate is (1-1) a (meth) acrylate having a cyclic ether skeleton, (1-2) a (meth) acrylate having an aromatic ring, or (1-3). A di (meth) acrylate having a bisphenol A skeleton can be contained, and a combination of two or more thereof may be contained. It is preferable that each of the above components (1-1) to (1-2) is a monofunctional (meth) acrylate having one (meth) acryloyl group.

(1-1) Examples of the (meth) acrylate having a cyclic ether skeleton include glycidyl (meth) acrylate, flufuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, and the like. (2-Methyl-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, γ-butyrolactone (meth) acrylate, dioxolan (meth) acrylate, dioxane glycol di Examples thereof include (meth) acrylate and oxetan (meth) acrylate, and one or more of these can be used. Among the cyclic ether skeletons, a 5- to 6-membered ring is preferable. The cyclic ether skeleton preferably has an oxygen number of 1. The cyclic ether skeleton preferably has 2 to 5 carbon atoms. Among the (meth) acrylates having a cyclic ether skeleton, tetrahydrofurfuryl (meth) acrylate is preferable.

(1-2) Examples of the (meth) acrylate having an aromatic ring include phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, and neopentyl glycol. Benzoate (meth) acrylate, ECH (epichlorohydrin) modified phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl (meth) acrylate and the like can be mentioned, and one or more of these can be used. Of these, (meth) acrylates having a phenoxy group are preferred. The phenoxy group preferably has a structure represented by the following formula (1).

In the formula, R represents an arbitrary substituent, for example, hydrogen, an alkyl group, or a hydroxyl group. Among R, hydrogen is preferable.

The number of aromatic rings is, for example, 1, 2, or 3, preferably one. As (1-2), it is preferable to remove (1-3).

Examples of the di (meth) acrylate having the (1-3) bisphenol A skeleton include (poly) ethoxy-modified bisphenol A di (meth) acrylate, (poly) propoxy-modified bisphenol A di (meth) acrylate, and the like. More than one can be used. Of these, (poly) ethoxy-modified bisphenol A di (meth) acrylate is preferred. Among the (poly) ethoxy-modified bisphenol A di (meth) acrylates, the compound represented by the following formula (2) is preferable. The m + n (that is, ethoxy equivalent) in the formula is preferably 1 to 40, more preferably 3 to 20, most preferably 5 to 15, and even more preferably 10. ^{R 1} and R ² in the formula may be independently hydrogen atoms or ₃ CH groups.

When the above-mentioned components (1-1) to (1-3) are used in combination, the content ratio thereof is (1): (1-2) when the whole component is 100 parts by mass. ): (1-3) = 10 to 90: 5 to 80: 1 to 30, more preferably 30 to 50:40 to 60: 5 to 20.

The content of the component (1) in the composition according to the present embodiment is preferably 60 to 99 parts by mass, more preferably 70 to 90 parts by mass, based on 100 parts by mass of the total of the components (1) to (4). , 75-85 parts by mass is most preferable.

The alkylborane-amine complex, which is the component (2) used in the present embodiment, is a complex obtained by coordinating an amine with alkylborane. The component (2) can act as a polymerization initiator for the (meth) acrylate.

Examples of such an alkylborane-amine complex include triethylborane-diaminopropane complex such as triethylborane-1,3-diaminopropane complex, triethylborane-diethylenetriamine complex, tributylborane-3-methoxy-1-propylamine complex, and tributylborane-. Examples thereof include 1,3-diaminopropane complex, triisobutylborane-1,3-diaminopropane complex, and one or more of these can be used. Among these, one or more of the group consisting of triethylborane-1,3-diaminopropane complex, triethylborane-diethylenetriamine complex, and tributylborane-3-methoxy-1-propylamine complex is preferable, and triethylborane-diethylenetriamine is preferable. Complexes are more preferred.

The amount of the component (2) used in the composition according to the present embodiment is preferably 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the components (1) to (4). Parts are more preferable, and 0.2 to 4 parts by mass are most preferable. (2) When the amount of the component used is 0.01 parts by mass or more, the adhesiveness is improved, and when it is 10 parts by mass or less, the curing reaction does not become too fast and the workability does not deteriorate.

The compound that undergoes an addition reaction with amine, which is the component (3) used in the present embodiment, is a compound that can act as a curing accelerator (also referred to as "deprotecting agent") for (meth) acrylate. The component (3) is distinguished from a compound that undergoes a substitution reaction with an amine. The present inventor focused on the addition reaction, which is a relatively slow reaction, and came up with the idea that the pot life of the composition can be appropriately secured by using the component (3).

As the component (3), those containing an acid anhydride are preferable, and those containing an acid anhydride monomer as at least a part of the monomer units in the polymer compound are more preferable. Preferably, 5 to 25% by mass, more preferably 8 to 25% by mass, and even more preferably 10 to 25% by mass of the monomer units in the polymer compound component are acid anhydride monomers. Good. (3) When the component is a polymer compound, it is considered that the steric hindrance becomes large or the diffusion rate becomes slow, which reduces the collision frequency between molecules in which an addition reaction occurs, and the pot life can be adjusted more appropriately. It is thought to be effective.

In the polymer compound, the number average molecular weight (Mn) is preferably 10,000 or more, more preferably 10,000 or more and 1,000,000 or less, and further preferably 10,000 or more and 100,000 or less. When the number average molecular weight is 10,000 or more, the toughness is improved.

The weight average molecular weight (Mw) of the component (3) is not particularly limited, but is preferably 10,000 or more and 1,000,000 or less, and more preferably 20,000 or more and 300,000 or less.

The ratio of Mw to Mn (Mw / Mn) in the component (3) is preferably 1 to 5, and more preferably 2 to 3.

In the polymer compound of the present embodiment, the molecular weight refers to an average molecular weight calculated as an average molecular weight per molecule. As the average molecular weight of this embodiment, the polystyrene-equivalent average molecular weight measured by GPC (gel permeation chromatography) was used. Specifically, the average molecular weight was determined by preparing a calibration curve with commercially available standard polystyrene using tetrahydrofuran as a solvent and using a GPC system (SC-8010 manufactured by Tosoh Corporation) under the following conditions. Both the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be quantified by this method.
Flow velocity: 1.0 ml / min
Set temperature: 40 ° C
Column configuration: Tosoh's "TSK guardcolum MP (xL)" 6.0 mm ID x 4.0 cm 1 piece, Tosoh's "TSK-GELMULTIPOREHXL-M" 7.8 mm ID x 30.0 cm (theoretical plate number 16,000) 2 pieces, 3 pieces in total (32,000 theoretical plates as a whole)
Sample injection volume: 100 μl (sample solution concentration 1 mg / ml)
Liquid transfer pressure: 39 kg / cm ²
Detector: RI detector

As an example of the component (3), a copolymer of a (meth) acrylic acid ester monomer, an aromatic vinyl monomer, and an acid anhydride monomer is preferable.

As the (meth) acrylic acid ester monomer, it can be selected from various (meth) acrylates as in the case of the above-mentioned component (1), but methyl (meth) acrylate can be preferably used. It should be noted that this (meth) acrylic acid ester monomer forms only a part of the polymer compound contained in the component (3) and is distinguished from the component (1). The content of the (meth) acrylic acid ester monomer is preferably 0.1 to 80% by mass, more preferably 1 to 60% by mass, still more preferably 3 to 50% by mass, based on the whole component (3). Most preferably, 5 to 35% by mass. When the content is 0.1% by mass or more, adhesiveness is likely to be exhibited, and when the content is 80% by mass or less, copolymerization with an acid anhydride or styrene is possible.

Examples of the aromatic vinyl monomer include styrene, vinyltoluene, divinylbenzene, α-methylstyrene, tert-butylstyrene, chlorostyrene and the like. Of these, styrene is preferred. The content of the aromatic vinyl monomer is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, and further 30 to 75% by mass based on (3) the entire component from the viewpoint of improving adhesion. It is preferably 50 to 75% by mass, most preferably 50 to 75% by mass.

As the acid anhydride monomer, an unsaturated dicarboxylic acid anhydride monomer is preferable. Examples of the unsaturated dicarboxylic acid anhydride monomer include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride and the like. Of these, maleic anhydride is preferred. The content of the acid anhydride monomer is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, still more preferably 10 to 25% by mass, based on the whole component (3).

Preferred examples of the component (3) include a styrene-methylmethacrylate-maleic anhydride copolymer (also referred to as Sty-MMA-MAH resin or SMM resin). Preferably, among the monomer units in the polymer compound component (copolymer) of the component (3), acid anhydride is 10 to 25% by mass, (meth) acrylic acid ester is 5 to 35% by mass, and aromatic. The group vinyl may be a combination of 50 to 75% by mass.

The content of the component (3) in the composition according to the present embodiment is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, based on 100 parts by mass of the total of the components (1) to (4). , 7 to 25 parts by mass is more preferable. If the content is 1 part by mass or more, the strength is improved, and if it is 30 parts by mass or less, the curing reaction does not become too fast and the workability does not decrease.

The metal-containing phosphate compound used in the present embodiment (4) has a function of controlling the activities of the components (2) and (3), and secures a pot life and is difficult to cover. It is a component that has the effect of ensuring the adhesive strength to the body.

Examples of the component (4) include metal phosphate, metal monohydrogen phosphate, and metal dihydrogen phosphate. Phosphoric acid is preferably orthophosphoric acid. Further, as such a metal, any metal capable of forming a salt with phosphoric acid can be used. Among the metals, one or more selected from alkali metals and alkaline earth metals are preferable, and lithium and / or sodium are more preferable.

The component (4) may be a monomer or a polymer. Examples of the monomers include trisodium phosphate, tripotassium phosphate, ammonium magnesium phosphate, hydroxyapatite, metal salt of acid phosphoxy (meth) acrylate monomer, metal salt of acid phosphoxidi (meth) acrylate monomer, and hydrogen phosphate. Examples thereof include disodium, dipotassium hydrogen phosphate, magnesium monohydrogen phosphate, calcium monohydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and the like. Among these, a compound having a (meth) acryloyl group is preferable. Among the compounds having a (meth) acryloyl group, a compound having a (meth) acryloyloxy group is preferable. As the compound having a (meth) acryloyloxy group, one or more selected from an acid phosphoxy (meth) acrylate monomer, an acid phosphoxidi (meth) acrylate monomer, or a mixture thereof is preferable. As the compound having a (meth) acryloyloxy group, a monomer of a compound having the following formula (3) is preferable.

Among the components (4), metal salts are preferable. As the metal salt of the compound having a (meth) acryloyloxy group, one or more selected from a metal salt of an acid phosphoxy (meth) acrylate monomer, a metal salt of an acid phosphoxidi (meth) acrylate monomer, or a mixture thereof is preferable. .. Among the metal salts of the acid phosphoxy (meth) acrylate monomer, the metal salt of the alkyl (meth) acrylate acid phosphate monomer is more preferable, and the metal salt of 2-hydroxyethyl (meth) acrylate acid phosphate monomer is further preferable.

Examples of the polymer contained in the component (4) include a polymer obtained by polymerizing any of the above monomers (polyphosphoric acid compound), and a metal salt of an acid phosphoxyalkyl (meth) acrylate polymer. Of these, metal salts of acid phosphoxyalkyl (meth) acrylate polymers are preferred. As such an acid phosphoxyalkyl (meth) acrylate polymer, a polymer of a compound having the following formula (3) is preferable.

Examples of the method for synthesizing the polymer contained in the component (4) include a method of radically polymerizing a carbon-carbon double bond of a compound having the following formula (3) or a salt thereof using a polymerization initiator.

Examples of the method of salting include a method of neutralizing by using a salt as a monomer, and a method of neutralizing by using a salt after making a polymer.

In the formula, A (plurality of independently if you) hydrogen atom, an alkyl group (preferably C ₁ ~ C ₆ alkyl group, more preferably methyl group), or an alkylhalo group (preferably C ₁ ~ C ₆ alkylhalo A group, more preferably a chloro C ₁ to C ₆ alkyl group, still more preferably a chloromethyl group). n is an integer from 1 to 6. k is an integer of 1 or 2. R ¹ may be a hydrogen atom or _three CHs.

Examples of the above-mentioned polymer include a polymer having the above-mentioned formula (3) as a monomer unit, and for example, a polymer of the following formula (4) is preferable.

A, n, k, and R ¹ in the equation are the same as in the equation (3), and i represents the number of repeating units and may be in the range of, for example, 10 to 100,000. In the case of a monomer unit of k = 2, one or more of the (meth) acrylate portions may be bonded to another monomer unit.

(4) The substance amount ratio of the metal to the P-OH group in the component is preferably 0.1 to 0.85 molar equivalent.

The amount of the component (4) used in the composition according to the present embodiment is preferably 0.1 to 10 parts by mass, preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the total of the components (1) to (4). More preferred.

The composition of the present embodiment may further contain an elastomer component in order to improve the adhesiveness. The elastomer component refers to a polymer substance having rubber-like elasticity at room temperature (for example, in the range of 5 to 35 ° C. specified in JIS Z8703: 1983), and a substance that can be dissolved or dispersed in a (meth) acrylic acid derivative monomer. preferable. It is preferable to remove the above-mentioned (1) component, (3) component, and (4) component from the elastomer component.

Examples of such elastomer components include (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer, (meth) acrylonitrile-butadiene-methyl (meth) acrylate copolymer, and methyl (meth) acrylate-butadiene-styrene copolymer. (MBS), (meth) acrylonitrile-styrene-butadiene copolymer, and various synthetic rubbers such as (meth) acrylonitrile-butadiene rubber (NBR), linear polyurethane, styrene-butadiene rubber, chloroprene rubber and butadiene rubber, natural Styrene-based thermoplastic elastomers such as rubber and styrene-polybutadiene-styrene-based synthetic rubber, olefin-based thermoplastic elastomers such as polyethylene-EPDM synthetic rubber, and urethane-based thermoplastic elastomers such as caprolactone type, adipate type and PTMG type, polybutylene terephthalate- Polypolytetramethylene glycol multi-block polymer and other polyester-based thermoplastic elastomers, nylon-polypolyblock copolymers and nylon-polyester block copolymers and other polyamide-based thermoplastic elastomers, 1,2-polybutadiene-based thermoplastic elastomers, and vinyl chloride-based Examples thereof include thermoplastic elastomers. One or more of these elastomer components may be used as long as they are compatible with each other.

Among these, (meth) acrylonitrile-butadiene rubber (NBR) is preferable in terms of solubility and adhesiveness to the (meth) acrylic acid derivative monomer.

The content of the elastomer component in the composition according to the present embodiment is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and further preferably 5 to 10 parts by mass with respect to 100 parts by mass of the total composition. preferable. If the content is 1 part by mass or more, the strength is improved, and if it is 30 parts by mass or less, the curing reaction does not become too fast and the workability does not decrease.

It is preferable to use the embodiment of this embodiment as a two-agent type composition. In the case of a two-dosage form, all the essential components of the composition of the present embodiment are not mixed during storage, and the composition can be divided into a first agent and a second agent. In a preferred embodiment, the first agent may contain at least the component (2) and the second agent may contain at least the components (1), (3), and (4) separately. In this case, both agents can be applied to the adherend at the same time or separately, contacted and cured to be used as a two-agent type composition. In a more preferred embodiment, the first agent is at least the (1-1) and (2) components, and the second agent is at least the components (1-2), (1-3), (3), and (4). ) Ingredients may be included respectively. The second agent may contain the component (1-1).

When the first agent and the second agent are mixed, the mixing ratio of the first agent and the second agent is preferably 1: 1 to 1:30, more preferably 1: 5 to 1:15 in terms of mass ratio. Most preferably 1: 8 to 1:12.

The composition of the present embodiment does not require accurate weighing of the two agents, and cures at room temperature even with incomplete weighing, mixing, and sometimes contact between the two agents. No ultraviolet light is required to cure the composition of this embodiment. The composition of the present embodiment is excellent in workability.

The composition of this embodiment can be used as a curable resin composition. Moreover, the composition of this embodiment can be used as an adhesive composition.

The adhesive composition of this embodiment is preferably used for an adherend. As the adherend, one or more of the group consisting of polyolefins such as polypropylene and polyethylene, cycloolefins, polystyrenes, fiber reinforced plastics, and metals is preferable. The fiber reinforced plastic is, for example, a plastic containing fibers. As the fiber, carbon fiber is preferable. As the plastic, polyolefin is preferable. As the metal, aluminum or zinc is preferable. The present embodiment has excellent adhesiveness to difficult-to-attach bodies such as polyolefins, metals, and fibrous-containing polyolefins.

Hereinafter, the present embodiment will be described with reference to Examples, but the present embodiment is not limited to these Examples. Each material used is as follows, and the unit of the amount used is shown in parts by mass. Some of the materials used may also be referred to herein by the abbreviations shown below. Further, in the present specification, the (meth) acrylate monomer may be abbreviated as "acrylic monomer". Unless otherwise specified, experiments were conducted in a temperature of 23 ° C. and a humidity of 50% in an RH environment.

[Material used]
[(Meta) Acrylate Monomer]
Tetrahydrofurfuryl methacrylate: Commercial product, abbreviation: THF-MA
Phenoxyethyl methacrylate: Commercial product, abbreviation: PO
2,2-Bis [4- (methacryloxypolyethoxy) phenyl] propane, ethoxy equivalent (m + n in formula (2)) = 10 mol: commercial product, abbreviation: BPE

[Alkylborane-amine complex and its control]
Triethylborane-diethylenetriamine complex, molecular weight 201.16: commercial product, abbreviation: TEB-DETA
Cumene Hydroperoxide: Commercial product, abbreviation: CHP

[Compounds that undergo an addition reaction with amines]
Styrene-methylmethacrylate-maleic anhydride copolymer (Sty-MMA-MAH resin, mass ratio Sty: MMA: MAH = 65: 21: 14, Mn = 63,000, Mw = 170,000): Commercial product, abbreviation: SMM, Mw / Mn = 2.7

[Phosphate compound]
JPA-M: Metal salt of 2-hydroxyethyl methacrylate acid phosphate (compound of formula (5) below) (Refer to M type in the table for the type of metal salt)

K in the formula represents an integer of 1 or 2. n = 1.

PEM: Polymer of metal salt of acid phosphoroxypolyoxyethylene glycol monomethacrylate (compound of formula (6) below) (see M type in the table for the type of metal salt), solid content concentration 10% by mass, abbreviation: PEM

PPM: Polymer of metal salt of acid phosphoroxypolyoxypropylene glycol monomethacrylate (compound of formula (7) below) (see M type in the table for the type of metal salt), solid content concentration 15% by mass, abbreviation: PPM

[Metallic reagents]
28% by mass sodium methoxide methanol solution
4.65 mass% lithium methoxydomethanol solution

[Elastomer]
Acrylonitrile-butadiene rubber: commercial product, abbreviation: NBR

[Other]
PP (talc): Injection-molded polypropylene test piece containing 20% by mass of talc, no surface treatment, commercially available
AL: Aluminum test piece A5052P, commercially available

[Examples / Comparative Examples]
The first agent and the second agent were prepared as follows according to the formulations shown in Tables 1 and 2, respectively.

The acrylic monomer and elastomer shown in the table were added to a single flask, heated and stirred at 60 ° C., cooled, and then the initiator was added, and the mixture was further stirred and then taken out to obtain the first agent.

For the second agent shown in the table, acrylic monomer, elastomer and SMM are added to a single flask, heated and stirred at 60 ° C., cooled and then taken out, and JPA-M in Table 1 or PEM or PPM in Table 2 is added. Then, the mixture was further stirred and then taken out to obtain a second agent. For JPA-M in Table 1 and PEM and PPM in Table 2, the above metal reagents according to the M type (metal type) in advance are equivalent to those shown in the M conversion amount column (that is, the M conversion amount is phosphoric acid). It was prepared so as to have a molar equivalent of the metal with respect to the P-OH group (solid content conversion value), and the solvent was distilled off.
JPA-M was obtained by using the above metal reagent for 2-hydroxyethyl methacrylate acid phosphate (compound of formula (5)). PEM was obtained by using the above metal reagent with respect to the polymer of acid phosphoroxypolyoxyethylene glycol monomethacrylate (compound of the following formula (6)). PPM was obtained by using the above metal reagent with respect to the polymer of acid phosphoroxypolyoxypropylene glycol monomethacrylate (compound of the following formula (7)).

The first agent and the second agent were mixed at a mass ratio of 1:10 to obtain adhesive compositions according to Examples and Comparative Examples, and their physical properties were evaluated. The results are also shown in Tables 1 and 2. In the table, the amount of components is a solid content conversion value.

†: No metal reagents were added.

Physical characteristics were measured as follows.

[Tensile shear strength]
According to JIS K6856: 1994, one side of a test piece (100 mm × 25 mm × 2 mmt) of the above-mentioned material is coated with a mixture of the first agent and the second agent at a mass ratio of 1:10, and then another test piece. (100 mm × 25 mm × 2 mmt) were laminated so that the overlapping area was 12.5 mm × 25 mm. At this time, the open time was 0 minutes when the coating was applied immediately after application, and the open time was 5 minutes when the coating was cured for 5 minutes after application. Then, the bonded test pieces were cured in a temperature of 23 ° C. and a humidity of 50% RH for 3 days to obtain a sample. The measurement on the sample was carried out at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. The value of the adhesive strength with an open time of 5 minutes is also shown as a "retention rate" percentage based on the value with an open time of 0 minutes.

In the measurement of tensile shear strength, the meanings of the symbols indicating the types of fracture are as follows. Regarding fracture, in terms of adhesiveness, M>C>CA> A is preferable in this order.
M: Material destruction
C: Aggregate fracture
CA: Thin cohesive failure (state in which the adhesive composition is thinly broken)
A: The interfacial fracture tilde symbol (~) indicates that the types on both sides were mixed.

The tensile shear strength against PP (talc) is preferably 2.5 MPa or more, so if it is 2.5 MPa or more, it was accepted.

The tensile shear strength against AL is preferably 4.0 MPa or more, so if it was 4.0 MPa or more, it was accepted.

All of the examples showed good adhesive strength against both PP and AL. This means that different types of PP and AL can be adhered well. In addition, in the examples, the retention rate after 5 minutes of application was also good, demonstrating that sufficient pot life can be secured.

On the other hand, Comparative Example 1 did not have adhesiveness to PP. In Comparative Example 2, adhesiveness to AL was not obtained. Comparative Example 3 did not cure and did not withstand practical use. Comparative Example 6 had a short pot life and was not practical.

This embodiment has excellent adhesiveness to difficult-to-adhere bodies such as polyolefins, a sufficient pot life can be secured, and adhesiveness of different materials can be obtained. This embodiment is also excellent in adhesiveness to an adherend such as a metal, particularly a metal having a high surface polarity such as iron, aluminum, and zinc.

Claims

A composition containing the following components (1) to (4).
(1) (Meta) acrylate (2) Alkylborane-amine complex (3) Compound that undergoes an addition reaction with amine (4) Phosphate compound containing a metal
(4) The composition according to claim 1, wherein the component is a compound having a (meth) acryloyl group or a polymer thereof.
(4) The composition according to claim 1 or 2, wherein the metal contained in the component is one or more selected from alkali metals and alkaline earth metals.
(4) The composition according to claim 3, wherein the metal contained in the component is lithium, sodium, or both.
(4) The composition according to any one of claims 1 to 4, wherein the ratio of the amount of substance of the metal to the P-OH group in the component is 0.1 to 0.85 molar equivalent.
(4) The composition according to any one of claims 1 to 5, wherein the amount of the component used is 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the components (1) to (4). ..
(4) The composition according to any one of claims 1 to 6, wherein the component is a monomer.
(4) The composition according to any one of claims 1 to 6, wherein the component is a polymer.
(1) The composition according to any one of claims 1 to 8, wherein the component comprises any one or more of the following.
(1-1) (Meta) acrylate having a cyclic ether skeleton (1-2) (Meta) acrylate having an aromatic ring (1-3) Di (meth) acrylate having a bisphenol A skeleton
(2) The component is one or more selected from the group consisting of triethylborane-1,3-diaminopropane complex, triethylborane-diethylenetriamine complex, and tributylborane-3-methoxy-1-propylamine complex. The composition according to any one of claims 1 to 9.
(2) The composition according to any one of claims 1 to 10, wherein the content of the component is 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of the components (1) to (4). ..
(3) The composition according to any one of claims 1 to 11, wherein the component contains an acid anhydride.
(3) The composition according to claim 12, wherein the component contains an acid anhydride monomer in a polymer compound having a number average molecular weight of 10,000 or more.
The composition according to claim 13, wherein 5 to 25% by mass of the monomer units in the polymer compound component is an acid anhydride monomer.
The composition according to any one of claims 12 to 14, wherein the acid anhydride is a copolymer of a (meth) acrylic acid ester, an aromatic vinyl, and an acid anhydride.
15. Of the monomer units in the copolymer, acid anhydride is 10 to 25% by mass, (meth) acrylic acid ester is 5 to 35% by mass, and aromatic vinyl is 50 to 75% by mass. The composition according to.
(3) The composition according to any one of claims 1 to 16, wherein the amount of the component used is 1 to 30 parts by mass with respect to a total of 100 parts by mass of the components (1) to (4).
A two-component composition having a first agent and a second agent, wherein the first agent contains at least the component (2) and the second agent contains at least (1), (3), and (4). The composition according to any one of claims 1 to 17, which contains an ingredient.
A curable resin composition containing the composition according to any one of claims 1 to 18.
An adhesive composition comprising the composition according to any one of claims 1 to 18.
A cured product of the composition according to any one of claims 1 to 18.
A method for adhering an adherend using the adhesive composition according to claim 20.
22. The method of claim 22, wherein the adherend is one or more of the group consisting of polyolefins, cycloolefins, polystyrenes, fiber reinforced plastics, and metals.
A bonded body bonded by the curable resin composition according to claim 19 or the adhesive composition according to claim 20.