JPS621772A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide the titled adhesive composition composed of a polymerizable material component containing a specific polymerizable monomer, a soluble polymer (excluding polyester), an organic peroxide and a reducing agent, and having excellent peel strength to various adherends, flexibility, durability, etc. CONSTITUTION:The objective composition is produced by compounding (A) a polymerizable material (e.g. methyl methacrylate) containing preferably (10-60wt% polymerizable monomer of formula CH2=CR1-CO-(OCH2CHR2)n-OR3 (R1 and R2 are H or CH3; R3 is H, 1-4C alkyl, etc.; n is 2-27) (e.g. phenoxydiethylene glycol methacrylate), (B) a soluble polymer (preferably acrylonitrile-butadiene rubber), (C) an organic peroxide (e.g. benzoyl peroxide) and (D) a reducing agent (e.g. N,N-dimethyl-p-toluidine). The weight ratios A:B:C:D are preferably (40-80):(1.0-10):(0.1-10). The components C and D are packed separately from the components A and B to form a two-pack type adhesive.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an adhesive composition that has excellent peel strength on various adherends such as plastic films, metal foils, paper, and cloth, and has good flexibility and durability. .

(Prior art) Various types of adhesives have been used in the past, depending on the material of the adherend and its purpose, such as organic solvent-based adhesives, water-based adhesives, and solvent-free adhesives, depending on the purpose. ing.

Adhesives containing solvents, such as organic solvent-based and water-based adhesives, can be used on adherends where the solvent is removed by penetration or volatilization, such as paper or cloth; however, adhesives such as plastic films, metal foils, etc. impermeable to solvents such as
Alternatively, it cannot be used for adherends that cannot be volatilized. Therefore, for combinations of adherends that do not pass through these solvents, heat seal bonding is performed after the solvent has been volatilized, or a solvent-free adhesive is used.

For example, it is known that a linear saturated polyester resin is dissolved in a solvent and used as an adhesive for adhesives such as polyester films and aluminum foils, which have relatively poor adhesive properties (Japanese Patent Publication No. 52-15092 ). This product is bonded by applying an adhesive to the adherend, evaporating the solvent, and then heat-sealing it. Polyester film/polyester film, aluminum foil/ The maximum peel strength of aluminum foil is 603g/crn and 615g/crn, respectively.
g/cmL, it cannot be said to have sufficient adhesive performance.

Similarly, adhesives made by dissolving chloroprene rubber in a solvent are also used to bond polyester films, aluminum foil, etc., but in general, solvents such as polyester films, aluminum foil, cloth, paper, etc. It is used in combination with adherends that volatilize, and is not used in combinations such as polyester film/polyester film or aluminum foil/aluminum foil.

On the other hand, known solvent-free adhesives include two-component reactive epoxy adhesives, cyanoacrylate adhesives, hot melt adhesives, and reactive acrylic adhesives.

Among these adhesives, reactive acrylic adhesives use organic peroxides and reducing agents as hardening agents.
It has shown rapid growth in recent years because it reacts at room temperature, exhibits strength that can be handled within minutes to tens of minutes, hardens even the protruding parts that come in contact with air, and has excellent adhesive properties in shear, impact, and peel strength. ing.

These reactive acrylic adhesives are
methacrylic acid alkyl ester as shown in 78,
Aku 4-nor thread picker, which is cured by contacting or mixing a solution of 2-hydroxyalkyl methacrylate and a butadiene elastomer, hydroperoxide, etc. with the reducing component of a redox catalyst, or Japanese Patent Publication No. 56 -9954 containing an acrylic monomer and tris(dimethylaminemethyl)phenol, a solution containing polyester resin, a reducing agent, etc. to adjust workability such as viscosity, and an accelerator containing hydroperoxide. Acrylic adhesives that are cured by contacting the adhesive are known.

However, the purpose of these reactive adhesives is mainly for adhesion of metals, and at the same time they have strong adhesion to metals and have the property that their cured products are hard.

Therefore, the plastic film that is the object of the present invention,
When bonding highly flexible adherends such as metal foil, cloth, paper, etc., and bending the bonded material, the adhesive layer becomes hard.
The adhesive layer will break, which poses a serious problem in practical use. Moreover, when cholera adhesive is used to bond polyester film, aluminum foil, etc., and the peel strength is measured,
The cohesive force of the adhesive layer is strong and the adhesion to the adherend is weak, resulting in interfacial peeling from the surface of the polyester film or aluminum foil, resulting in disadvantages such as insufficient adhesive strength.

As mentioned above, conventionally known adhesives are capable of bonding various adherends with a single type of adhesive, and have good workability and exhibit strength within a few minutes to several tens of minutes at room temperature. The reality is that there are no drugs available.

(Problems to be Solved by the Invention) The adhesive composition of the present invention improves the drawbacks of conventional adhesives as described below.

(1) With conventional adhesives, it was difficult to bond adherends made of different materials such as plastic film, metal foil, paper, and cloth with a single type of adhesive, but the adhesive composition of the present invention It is possible to bond these various adherends with one type of adhesive, and it is especially effective for polyester film and aluminum foil, for which conventional adhesives have not been able to provide sufficient peel strength. It shows the peel strength.

(2) The main purpose of conventional reactive acrylic adhesives is metal adhesion, and the uncured adhesive layer is very hard, but the adhesive composition of the present invention is extremely flexible. It provides a cured product with rich properties.

(3) Conventionally, plastic film 1 metal 7I31
When trying to bond various adherends such as paper or cloth with a single type of adhesive, a rubber-based solvent-based adhesive is used. Although it had a drawback of poor durability, the adhesive composition of the present invention has extremely excellent durability.

(4) Among conventionally known adhesives, rubber adhesives can bond various adherends with one type of adhesive, but it takes several hours to several tens of hours to bond. There was a problem with work speed. The adhesive composition of the present invention solves all of these drawbacks, allows various adherends to be bonded with a single type of adhesive, and is highly workable, allowing bonding in a few minutes to several tens of minutes at room temperature. It is a good adhesive.

(Means for Solving the Problems) As a result of intensive studies to improve the above-mentioned problems, the present inventor found that conventional rubber-based solvent-based adhesives or reactive acrylic adhesives could not be used. The present inventors have discovered an adhesive composition that exhibits excellent adhesive performance and workability, and have completed the present invention.

That is, the adhesive composition of the present invention has the general formula % (where R1 and R2 are hydrogen or a methyl group, R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, or a phenyl group, or Contains a polymerizable monomer (hereinafter abbreviated as GA monomer) having an alkyl group having 1 to 4 carbon atoms (enyl group, n represents an integer of 2 to 27), and further contains a soluble polymer (with the exception of polyester). ), containing an organic peroxide and a reducing agent.

This adhesive composition is fast-curing, can bond various adherends such as plastic film, metal foil, paper, and cloth with a single adhesive, has excellent peel strength, and has good flexibility and durability. It is.

The most distinctive feature of the composition of the present invention is that it uses a GA monomer represented by the above general formula as a polymerizable substance. Therefore, the adhesive composition of the present invention is different from conventional reactive acrylic adhesives. Forms an extremely flexible cured product that was previously unimaginable, and also exhibits excellent peel strength and durability against various adherends such as plastic film, metal foil, paper, and cloth, especially when used with conventional adhesives. It exhibits significantly superior adhesion to polyester films, aluminum foil, etc., which were previously difficult to adhere to. Furthermore, it is possible to bond even combinations of adherends that would be difficult to achieve with conventional rubber adhesives, and its workability is very good as it can be cured in a few minutes to several tens of minutes at room temperature.

As described above, the present invention is an acrylic adhesive composition containing GA monomer as a polymerization component, but GA is used as a polymerizable substance.
Although the monomer alone may be used, it is preferable to include other monomers or polymerizable substances such as oligomers in order to prevent residual adhesion on the surface when the composition is cured.

In the above general formula, when n is relatively large, the GA monomer is solid at room temperature, but by using other polymerizable substances together, the GA monomer dissolves in the polymerizable substance, resulting in favorable adhesion. A drug composition is obtained.

A preferred embodiment of the adhesive composition of the present invention is as follows: (B) soluble polymer 5-60% by weight, more preferably 10-50% by weight; (C) organic filtrate; 0.1 to 20% by weight of oxide, more preferably 1.0 to 10% by weight, (D+ 0.05 to 15% by weight of reducing agent capable of generating radicals in contact with the organic peroxide, more preferably is 0
．． Contains 4 components (A), (B), (C) and (D) of 1-10 weight ratio,
By bringing an organic peroxide into contact with a reducing agent, it cures in minutes to tens of minutes at room temperature, creating a flexible cured product that was unimaginable with conventional acrylic reactive adhesive technology. Moreover, it exhibits excellent peel strength against plastic films, metal foils, paper, cloth, etc.

In this embodiment, component (A) contains 20 to 94 weight percent, particularly preferably 40 to 80 weight percent, of a polymerizable substance having at least one unbent double bond in the molecule, The material contains from 5 to 70 parts by weight, particularly preferably from 10 to 60 parts by weight, of GA monomer.

When the content of GA monomer increases by more than 70% by weight, the cured product produced by the reaction becomes sticky and too soft.
On the contrary, the adhesive strength becomes weaker.

When the weight ratio is less than 5, the adhesion to plastic films and metal foils is weak. When R3 in the GA monomer is an alkyl group or a phenyl group having an alkyl substituent, the number of carbon atoms in the alkyl group is 1 to 4, and if it is 5 or more, the cured product becomes soft and sufficient adhesive strength cannot be obtained. .

Further, n is in the range of 2 to 27, and if it exceeds this value, the adhesion will deteriorate and at the same time the viscosity of the final formulation will increase, resulting in poor workability. The number of n does not have to be a constant pure product, and the object of the present invention can be achieved as long as the monomer having the above structure with different numbers of n is mixed and the average number of n is 27 or less.

Examples of the GA monomer having the structure described above include:
methoxydiethylene glycol (meth)acrylate,
Methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol up to n=27 (
Meth)acrylate, hereinafter, includes polyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)azilylate, polypropylene glycol (meth)acrylate, etc. in which the number n falls within the above range. These GA monomers may be used alone or in combination with other polymerizable substances, and as long as the ratio of the GA monomers used is within the above range, the object of the present invention can be achieved.

Examples of polymerizable substances other than the GA monomer that can be used include monomers or oligomers, such as [4J, for example, alkyl esters of acrylic acid or methacrylic acid,
-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, dimethylaminoethyl (ivy) acrylate, diethylaminoethyl (ivy) acrylate, acid phosphogyethyl methacrylate, anddophospooxypropyl methacrylate, glycidyl methacrylate Acrylic monomers such as acrylate, urethane acrylate, epoxy acrylate,
Examples include oligomers such as polyester acrylate. These monomer cases or the first nogomer can be used in any combination that does not impede the purpose of the present invention within the range of the ratio of the remaining amount used after subtracting the GA monomer from the polymerizable material.

The soluble polymers contained in the adhesive composition used in the present invention are acrylonitrile-butadiene rubber, (meth)acrylate copolymer, polyurethane, styrene-butadiene rubber, chloroprene rubber, butadiene rubber, natural comb, methyl methacrylate-butadiene-styrene. Examples include copolymers, methyl methacrylate-butadiene-acrylonitrile-styrene copolymers, styrene-acrylonitrile copolymers, acrylonitrile-styrene-butadiene copolymers, polymethyl methacrylate, phenolic resins, among others, acrylonitrile-butadiene rubber. , (meth)acrylic acid ester copolymers are preferred.

Two or more types of polymers can be used in combination as long as they have good compatibility.

The proportion of polymer in the composition is from 5 to 60 parts by weight, more preferably from 10 to 50 parts by weight.

The organic peroxides used in the present invention include benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, tertiary-butyl peroxide, pinene hydroperoxide, para-menthane hydroperoxide, diimpropyl hydroperoxide, and cumene hydroperoxide. peroxide,
Examples include, but are not limited to, diisobrobylbenzene dihydroperoxide and tertiary butyl hydroperoxide.

The typical amount of organic peroxide used in the adhesive composition is 0.
1 to 20% by weight, and if it is less than 0.1% by weight, the curing speed is low, and on a 20% by weight board, the adhesiveness to plastic films and metal foils decreases, making it undesirable.

The usage of organic peroxide in the present invention is, for example, as follows.

(a) Pre-apply organic peroxide as it is, or by dissolving it in a solvent such as acetone, ethyl acetate, 1.111-) +) chloroethane, or dispersing it in a plasticizer such as dioctyl phthalate or dibutyl phthalate. How to use it: apply it to the body, then apply the following composition containing a reducing agent and cure by reaction.

(b) A composition containing a polymerizable substance and a reducing agent, in which one composition is an organic peroxide dissolved in a polymerizable substance (polyester resin and/or stabilizer, etc. are also dissolved as necessary). A method of reaction curing by contacting with a polyester resin and/or a stabilizer (if necessary).

Examples of the reducing agent used in the present invention include tertiary amines, oxime compounds, thiuram compounds, thiourea derivatives, and metal salts.

Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, triamylamine, ethylenediethanolamine, and N.

Examples include N-dimethyl para-toluidine.

Examples of oxime compounds include methyl ethyl ketone oxime, methyl isobutyl ketone oxime, acetophenone oxime, and P,P'-dibenzoylquinone dioxime. Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, diethylthiourea, digtylthiourea, tetramethylthiourea, ethylenethiourea, and thiobarbylic acid. Examples of the metal salt include cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate, and titanium acetylacetonate. Several kinds of these reducing agent components can be used in combination depending on the purpose.

The typical amount of reducing agent used in the adhesive composition is 0.05 to 1
It is 5% by weight, more preferably 0.1 to 10% by weight.

As described above, the adhesive composition of the present invention contains a GA monomer and, if necessary, other polymerizable substances, a soluble polymer, an organic peroxide, and a reducing agent as essential components. It is also possible to use paraffin wax and other known additives such as various antioxidants and polymerization inhibitors for the purpose of improving stability.

Furthermore, depending on the purpose, it is also possible to use plasticizers, fillers, thickeners, colorants, etc.

In addition, the amount M of the usage ratio of each component mentioned so far is:
It is the proportion of the total composition that ultimately acts as an adhesive. In other words, when it is divided into two liquids, it is the ratio of the total of those two liquids.

As mentioned above, the adhesive composition of the present invention is one type,
It is possible to bond plastic films, metal foils, paper, cloth, etc., and also exhibits strong peel strength against polyester films and aluminum foils, which were relatively difficult to bond with in the past, as well as resistance to heat deterioration and moisture deterioration. The present invention provides a new high-performance adhesive that has excellent adhesion over a wide temperature range and is highly flexible, making a major contribution to industry by improving productivity.

(Example) The present invention will be further explained by examples.

Example 1 The adhesive composition had the formulation shown in Table 1, and GA monomer, polymerizable substances other than GA monomer, and soluble polymer were placed in 11 flasks and dissolved for 24 hours with stirring to form a uniform solution. did. Furthermore, an organic peroxide and a polymerization inhibitor were added to liquid A, and an accelerator was added to liquid B to form an adhesive composition Nα1.
~Nα5 was adjusted.

Example-2 The adhesive composition prepared in Example-1 was mixed with liquid A and liquid B at a ratio of 1:1, and a broken body of 110 cm x 10
cm), apply the adhesive evenly to a thickness of about 50 μm (-sandwich it between 3-inch thick polyethylene plates,
2 g in a constant humidity room at 23°C and 50 RH.
It was cured for 4 hours.

The adhesive composition of the present invention was then cut into 25-inch pieces, and the peel strength was measured using an Instron tensile tester model 1123 at a tensile speed of 50 mm/min. It can be seen that it has excellent adhesion to broken adherends.

In addition, the set times listed in Table 2 are for iron test pieces (8S
-4x, 100■ x 25 tone x 1.6m+) with wrap length 1
At 2.5■, the tensile shear strength is 5 Kg / 3.2 c when bonded at 23°C and 50% RH! The time when the test was completed was taken as the set time.

Example 3 The moisture deterioration resistance at 60° C. and 95% RH and the heat deterioration resistance at 110° C. of the polyester film 1 cotton canvas adhesive test piece prepared by the method of Example 2 were measured in terms of peel strength.

For comparison, we simultaneously evaluated the @layer performance of a commercially available chloropre/rubber-based solvent-type adhesive composition used for adhering polyester fill 91 paper, polyester film 1 cloth, etc. It was found that both heat deterioration resistance and performance were significantly inferior compared to the adhesive composition of the present invention.

These results are shown in Table-3.

Table 3 Example 4 Liquid A of the adhesive composition prepared in Example 1 and Bi were mixed at a weight ratio of 1:1 to create a sheet-like cured product with a thickness of 211II, which was manufactured using JIS K630101. Dumbbells were made and their tensile strength and elongation were measured.

A hardness was measured by stacking three sheet-like cured products. The results are shown in Table 4.1. However, it has been found that the cured product of the adhesive of the present invention is much more flexible than the cured product of conventional reactive acrylic adhesives.

Comparison row-1 The peel strength of various adherends was measured using the commercially available two-component reactive acrylic adhesive composition No. 6 in the same manner as in test row-2. The results and cent times are listed in Table-2. did. It can be seen that such conventional reactive acrylic adhesive compositions cannot provide sufficient adhesion to various adherends.

In addition, as in Example 4, the results of measuring the tensile strength, elongation, and A hardness of the cured adhesive compositions are listed in Table 4. It can be seen that cured products of conventional reactive acrylic adhesive compositions cannot provide cured products with high flexibility.

Comparative Example 2 An adhesive composition containing no GA monomer was prepared in the same manner as in Example 1 according to the recipe in Table 5. The peeling 'j'D, degree and cent time, tensile strength, elongation and A hardness of the cured adhesives of various adherends of No. 7 and No. 8 of this adhesive cured product were measured in row-2 and row-4. Measured in the same manner. The results are shown in Table-2 and Table-4.

Abbreviation MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate B
PO: Penzoyl peroxide DMPT: NN-dimethyl-p-toluidine CHP: 17 hydroperoxide TMTU: Tetramethylthiobromine pBQ: p-benzoquino/ Q: Hydroquinone (effects of the invention) Adhesive composition according to the invention It is possible to bond adherends that were previously difficult to bond, such as polyester film, at room temperature in a short time, with good durability, and firmly, making it possible to streamline work and improve the reliability of the bonded product. In addition, since it does not use a solvent unlike conventional adhesives, it has the effect of preventing deterioration of the working environment, and its industrial applicability is extremely large.

Patent applicant Denki Kagaku Kogyo Co., Ltd. Procedural amendment July 23, 1985 Director of the Patent Office Michibe Uga 1, Indication of the case 1985 Patent Application No. 140275 2 Name of the invention Adhesive composition 6 Relationship with the case of the person making the amendment Patent applicant address 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Column 5 of the detailed description of the invention in the specification Contents of amendment (1) Page 15, line 18 of the specification Correct "polyester resin" to "soluble polymer".

(2) In the first line of page 16 of the specification, "polyester resin" is corrected to "soluble polymer" (2).

(3) Delete "N■: Panazome naphthenate," in the 8th line from the bottom of page 19 of the specification.

(4) Delete "Commercially available polyester resin: Trade name Byron 106 Toyobo Co., Ltd." from the bottom line of page 19 of the specification.

(5) “ILM 1 cotton canvas” on page 22, line 6 of the specification
is corrected to "ilm/cotton canvas."

(6) “Polyester 74” on page 22, line 6 of the specification
21 paper” was corrected to “polyester film/paper”.

(Correct "Polyester film/cloth" on page 22, line 7 of the specification.)

Claims (1)

[Claims] General formula CH_2=CR_1-CO-(OCH_2CHR_2) as a polymerizable substance component
-_nOR_3 (However, R_1 and R_2 are hydrogen or a methyl group, R_3 is hydrogen or an alkyl group having 1 to 4 carbon atoms, or a phenyl group, or a carbon number 1
phenyl group with ~4 alkyl groups, n is 2-27
An adhesive composition characterized in that it contains a polymerizable monomer represented by (representing an integer of ), and further contains a soluble polymer (excluding polyester), an organic peroxide, and a reducing agent.