JP3205876B2 - Composite and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite and a method for producing the same, and more particularly, to a composite having improved adhesion between a substrate and an adhesive or a matrix resin, and a method for producing the same.

[0002]

2. Description of the Related Art A number of methods have been proposed for improving the adhesion of a substrate to an epoxy or polyester adhesive or matrix resin. Such prior art techniques include, for example, methods of increasing the surface area by mechanical means such as rubbing or corroding the surface of the substrate to which the adhesive is applied, thereby improving adhesion. Such methods require extra processing steps and are unsatisfactory in that they adversely affect the substrate.

[0003] Methods have also been proposed for improving the adhesion of substrates to adhesives by subbing the unmodified surface of the substrate with a chemical primer, and in many cases significantly improving the adhesion to various substrates. However, this method also has no effect on the combination of certain adhesives or matrix resins with certain substrates. For example, when using epoxy-based or polyester-based adhesives or matrix resins for substrates such as polyester, polyolefin, and metal, even if the surface of the substrate is treated with a chemical primer, the adhesive strength, peel strength, or water resistance In this respect, it is not satisfactory.

[0004] In order to achieve satisfactory results, the surface must be multi-layer treated or special chemical primers must be used, which requires an extra treatment step or requires very expensive special chemicals. The drawback is that primers increase production costs.

An object of the present invention is to provide a composite excellent in adhesive strength and water resistance and a method for producing the same by solving the above-mentioned problems of the prior art.

[0006]

The main structure of the composite of the present invention adopted to achieve the above object is represented by the following formula:

Embedded image (In the formula, R ₁ represents a lower alkyl group or a lower alkoxy group.
Represents) or an expression

Embedded image (Wherein R ₂ and R ₃ represent a hydrogen atom, a lower alkyl group or
Represents a lower alkoxy group) or a formula

Embedded image (Wherein R ₄ and R ₅ represent a hydrogen atom, a lower alkyl group or a lower alkyl group)
X represents an oxygen atom or a methylene group, respectively.
One or more than the group of organic diisocyanates represented by
The above is selected, and in the presence of a carbodiimidization catalyst,
And use alicyclic ethers at a concentration of 10% by weight or less.
Polycarbodii prepared from diisocyanate solution
Polycarbodiimide solution containing amide (A) and / or
Is the expression

Embedded image (R ₁ represents a lower alkyl group or an alkoxy group)
Carbodiimidation from organic diisocyanate
In the presence of a medium, using a chlorinated aliphatic hydrocarbon as a solvent,
From organic diisocyanate solution with a concentration of 15% by weight or less
Polycarbodiimide containing manufactured polycarbodiimide
Characterized in that one substrate treated with a solution (B) and further heat-treated is bonded to another substrate with an epoxy-based polymer or a polyester-based polymer, or the above-mentioned polycarbodiimide Solution (A) and / or
A substrate treated with the polycarbodiimide solution (B) and further heat-treated is contained in an epoxy polymer or polyester polymer as a matrix resin.

The main structure of the method for producing the composite of the present invention adopted to achieve the above object is that the substrate of the composite is prepared by using the above polycarbodiimide solution (A) and / or
After being treated with the polycarbodiimide solution (B) and further heat-treated, it is produced by using an epoxy polymer or a polyester polymer as an adhesive or a matrix resin.

Namely, the inventors of the present invention, when using an adhesive or matrix resin of epoxy or polyester, to solve the above has been pointed out conventionally problems, a result of intensive studies, the raw material Organic diisocyanate
Elaborate on the type of salt, its concentration or solvent
By treating with a high-molecular-weight polycarbodiimide solution obtained by the above, and using a substrate obtained by further heat treatment, it has been found that a composite having excellent adhesive strength and water resistance can be obtained, and the present invention Completed.

Hereinafter, the present invention will be described in detail.

The substrate used in the present invention includes an adherend made of a polymer material, an inorganic material, a metal material, or the like. The adherend can withstand a heat treatment temperature described later, for example, a temperature of 70 ° C. or more. As long as it is sufficient, specifically, a polymer material such as a polyester film, a polyamide film, a polyimide film or a polycarbonate film, an inorganic material such as glass or ceramic, or copper, iron, brass, stainless steel, aluminum or zinc, etc. Metal materials can be mentioned.

[0011] The fiber as a substrate includes, for example, glass fiber, rock wool, steel fiber, aramid fiber,
There are polyester fibers, ceramic fibers, carbon fibers, and the like, and the filler as a substrate includes, for example, mica, vermiculite, calcium carbonate, barium sulfate, silica powder, calcium silicate, and the like.

[0012] In the present invention, although the substrate is being processed by the polycarbodiimide solution (A), as the organic diisocyanate which is a raw material compound of the polycarbodiimide solution (A), as described above, wherein

Embedded image (Wherein, R ₁ represents a lower alkyl group or a lower alkoxy group), or

Embedded image (Wherein R ₂ and R ₃ represent a hydrogen atom, a lower alkyl group or a lower alkoxy group), or

Embedded image Wherein R ₄ and R ₅ represent a hydrogen atom, a lower alkyl group or a lower alkoxy group, and X represents an oxygen atom or a methylene group, respectively. The polycarbodiimide solution (A) contains the polycarbodiimide obtained by reacting these organic diisocyanates in an alicyclic ether in the presence of a carbodiimidation catalyst.

As the organic diisocyanate represented by the above general formula, specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2
A mixture of 4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,
4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,
4'-diphenyl ether diisocyanate, 3,3 '
-Dimethyl-4,4'-diphenyl ether diisocyanate, 0-tolidine diisocyanate, and the like.

The alicyclic ether, which is a solvent for the reaction of the above organic diisocyanate, is preferably a liquid at room temperature and has two or less ether bonds in the molecule. Specifically, tetrahydrofuran, dioxane , Tetrahydropyran or a mixed solvent thereof, among which tetrahydrofuran is preferred.

When the organic diisocyanate of the type described above is used, polycarbodiimide solution
The concentration at the time of producing the liquid (A) is 10% by weight or less, preferably 7% by weight or less. The solution (A) thus obtained is a polycarbodiimide solution having a high molecular weight and good storage stability.

In the present invention, the substrate is treated with the polycarbodiimide solution (A) and / or the polycarbodiimide solution (B). The organic diisocyanate used as a raw material compound of the polycarbodiimide solution (B) is as follows. , As described above, the expression

Embedded image (Wherein R ₁ represents a lower alkyl group or a lower alkoxy group), and the polycarbodiimide solution (B) is obtained by converting the organic diisocyanate to a chlorinated aliphatic carbon in the presence of a carbodiimidization catalyst. It contains polycarbodiimide obtained by reacting in hydrogen.

As the organic diisocyanate represented by the above general formula, specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2
A mixture of 4-tolylene diisocyanate and 2,6-tolylene diisocyanate or 1-methoxyphenyl-2,4
-Diisocyanate and the like.

The chlorinated aliphatic hydrocarbon used as a solvent in the reaction of the organic diisocyanate preferably has a boiling point of 80 ° C. or higher, and specifically includes pentachloropropane, 1,2-dichloroethane, , 1,1-
Examples thereof include trichloroethane, 1,1,2,2-tetrachloroethane, tetrachloroethylene, trichloroethylene, and a mixed solvent thereof.

When the above-described organic diisocyanate is used, the polycarbodiimide solution may be used.
The concentration at the time of producing the liquid (B) is 15% by weight or less, preferably 10% by weight or less. The solution (B) thus obtained is a polycarbodiimide solution having a high molecular weight and good storage stability.

Next, the substrate is treated with the polycarbodiimide solution thus obtained, followed by heat treatment. The treatment of the substrate with the polycarbodiimide solution
It can be performed by a general method such as coating, dipping, spraying, etc., and the heat treatment is performed at a temperature of 70 ° C. or more,
What is necessary is just to carry out at the temperature of 0 to 250 degreeC.

An epoxy polymer or a polyester polymer is used as an adhesive or a matrix resin for the substrate after the treatment with the polycarbodiimide solution and the heat treatment. There is. Incidentally, as the epoxy polymer or the polyester polymer, those commercially available as an adhesive or a matrix resin can be used.

First, when an epoxy polymer or a polyester polymer is used as an adhesive, an epoxy polymer or a polyester polymer may be applied to a substrate and then adhered to another substrate. . At this time, as the other substrate, the same material as the above-mentioned substrate can be used, and this material may or may not be treated with the polycarbodiimide solution, and may be treated with heat. It is not necessary. In this case, the substrate is mainly selected from an adherend made of a polymer material, an inorganic material, a metal material, or the like.

On the other hand, when an epoxy polymer or a polyester polymer is used as the matrix resin,
The substrate may be impregnated with the epoxy polymer or polyester polymer by coating or spraying, and then cured, or the substrate and the epoxy polymer or polyester polymer may be mixed or kneaded. In this case, as the substrate, for example, glass fiber, rock wool, steel fiber, aramid fiber, polyester fiber, fiber such as ceramic fiber or carbon fiber, or, for example, mica,
It is mainly selected from fillers such as vermiculite, calcium carbonate, barium sulfate, silica powder and calcium silicate.

Next, the present invention will be described in more detail with reference to examples.

[0025]

Preparation Example 1 of Polycarbodiimide Solution 54 g of a mixture of 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate (mixing ratio: 80:20, hereinafter abbreviated as TDI) was placed in 500 ml of tetrachloroethylene to prepare a carbodiimidation catalyst (1). -Phenyl-3-methylphospholene oxide) at 120 ° C for 4 hours to obtain a polycarbodiimide solution. produced
The molecular weight of polycarbodiimide is 1.6 × 10 ⁴ (G
(Polystyrene conversion value by PC), and from this molecular weight
The degree of polymerization is 120.

[0026]

Preparation Example 2 of Polycarbodiimide Solution 10 g of 4,4'-diphenylmethane diisocyanate was reacted in 220 ml of tetrahydrofuran with 0.02 g of the same carbodiimidization catalyst as in Example 1 at 67 ° C. for 17 hours to obtain a polycarbodiimide solution. Manufactured polycarbodiy
The molecular weight of the mid is 2.1 × 10 ⁴ (However, police
Styrene conversion value), and the polymerization degree from the molecular weight is 100
Becomes

[0027]

[Preparation Example 3 of Polycarbodiimide Solution] 25 g of TDI was reacted in 440 ml of tetrahydrofuran with 0.062 g of the same carbodiimidization catalyst as in Example 1 at 60 ° C. for 7 hours to obtain a polycarbodiimide solution. produced
The molecular weight of polycarbodiimide is 8.1 × 10 ³ (G
(Polystyrene conversion value by PC), and from this molecular weight
The degree of polymerization is 60.

[0028]

Example 1 A 1.6 mm-thick copper plate was brush-coated with the polycarbodiimide solution of Production Example 1 above and heated at 100 ° C. for 3 hours.
Heat treated by drying for hours. Using Araldite AW106 (Ciba Geigy) as an adhesive,
The film was cured by clipping at 0 ° C. for 20 minutes, and the tensile shear peel strength was measured.

[0029]

Comparative Example 1 A sample not treated with the polycarbodiimide solution was prepared in the same manner as in Example 1, and the tensile shear peel strength was measured.

[0030]

Example 2 The polycarbodiimide solution of Production Example 2 was sprayed on a 1.6 mm thick copper plate, the solvent was removed at room temperature, and heat treatment was performed at 70 ° C. for 10 hours. Using Araldite AW106 (Ciba Geigy) as an adhesive,
The film was cured by clipping at 00 ° C. for 20 minutes, and the tensile shear peel strength was measured.

[0031]

Comparative Example 2 Using a copper plate sprayed with a polycarbodiimide solution in Example 2, a solvent was removed from the polycarbodiimide solution while maintaining the temperature at room temperature, and a sample was prepared in the same manner except that no heat treatment was performed. The tensile shear peel strength was measured.

[00324]

Example 3 A copper plate having a thickness of 1.6 mm was immersed in the polycarbodiimide solution of Production Example 3 to remove the solvent, and then heat-treated at 150 ° C. for 1 hour. Using Araldite AW106 (Ciba Geigy) as an adhesive, the composition was clipped and cured at 100 ° C. for 20 minutes, and the tensile shear peel strength was measured.

[0032]

Example 4 A 1.6 mm-thick stainless steel plate was brush-coated with the polycarbodiimide solution of Production Example 1 to give
Heat treatment was performed by drying at 1 ° C. for 1 hour. Using Araldite AW106 (Ciba Geigy) as an adhesive, the composition was clipped and cured at 100 ° C. for 20 minutes, and the tensile shear peel strength was measured.

[0033]

Example 5 A 100 μm-thick polyethylene terephthalate film was brushed with the polycarbodiimide solution of Production Example 1 and dried at 150 ° C. for 2 hours.
Heat treatment was performed. Using polyester resin for FW,
The film was cured by clipping at 150 ° C. for 1 hour, and the tensile shear strength was measured.

[0034]

Comparative Example 4 A sample was prepared in the same manner as in Example 5 except that the sample was not treated with the polycarbodiimide solution, and a tensile shear peel test was performed.

[0035]

Example 6 A heat treatment was performed by spraying the polycarbodiimide solution of Example 1 on a carbon cloth which had been sufficiently washed with a solvent to remove a sizing agent, and dried at 100 ° C. for 3 hours. Using Epicoat 828 (Yuika Shinil Epoxy Co.) as an adhesive (matrix resin), this was clipped and cured at 150 ° C. for 1 hour, and a 180 ° peel test was performed.

[0036]

Comparative Example 5 A sample was prepared in the same manner as in Example 6, except that the sample was not treated with the polycarbodiimide solution.
A 0 ° peel test was performed.

[0037]

Example 7 Using the samples prepared in Example 1 and Comparative Example 1, a boiling test (a sample was immersed in boiling water for 5 hours and a shear peel strength test was performed) was performed.

Table 1 shows the above results.

[Table 1]

[0039]

According to the present invention, a stable high molecular weight polycarbodiimide solution can be obtained very easily and easily by carefully devising the kind, concentration, solvent and the like of the organic diisocyanate used as a raw material. By treating a substrate in which a coalesced or polyester-based polymer is used as an adhesive or a matrix resin of a composite material, a composite having adhesive strength and water resistance that cannot be obtained by a conventional method is obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09J 167/02 C09J 167/02 // C08G 18/02 C08G 18/02 73/00 73/00 (56) References JP JP-A-2-117829 (JP, A) JP-A-3-2261 (JP, A) JP-A-1-308441 (JP, A) JP-A-3-2259 (JP, A) A) JP-A-1-174557 (JP, A) JP-A-4-202561 (JP, A) JP-A-2-292316 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C08L 63/00-63/10 C08L 67/02-67/03 C08K 9/04 C09J 5/02 C09J 163/00-163/10 C09J 167/02-167/03 C08G 18/02 C08G 73/00

Claims (16)

(57) [Claims] (1) a compound represented by the formula : (In the formula, R ₁ represents a lower alkyl group or a lower alkoxy group.
Represents) or the formula : (Wherein R ₂ and R ₃ represent a hydrogen atom, a lower alkyl group or
It represents a grade alkoxy group), or the formula ## STR3 ## (Wherein R ₄ and R ₅ represent a hydrogen atom, a lower alkyl group or a lower alkyl group)
X represents an oxygen atom or a methylene group, respectively.
One or more than the group of organic diisocyanates represented by
The above is selected, and in the presence of a carbodiimidization catalyst,
And use alicyclic ethers at a concentration of 10% by weight or less.
Polycarbodii prepared from diisocyanate solution
Polycarbodiimide solution containing amide (A) and / or
Is, the formula: 4] (R ₁ represents a lower alkyl group or an alkoxy group)
An organic diisocyanate over preparative being, touch carbodiimidization
In the presence of a medium, using a chlorinated aliphatic hydrocarbon as a solvent,
From organic diisocyanate solution with a concentration of 15% by weight or less
Polycarbodiimide containing manufactured polycarbodiimide
A composite obtained by bonding one substrate treated with a solution (B) and further heat-treated to another substrate with an epoxy-based polymer or a polyester-based polymer. 2. A formula: 5] (In the formula, R ₁ represents a lower alkyl group or a lower alkoxy group.
Represents) or the formula : (Wherein R ₂ and R ₃ represent a hydrogen atom, a lower alkyl group or
Represents a grade alkoxy group), or a formula: 7] (Wherein R ₄ and R ₅ represent a hydrogen atom, a lower alkyl group or a lower alkyl group)
X represents an oxygen atom or a methylene group, respectively.
One or more than the group of organic diisocyanates represented by
The above is selected, and in the presence of a carbodiimidization catalyst,
And use alicyclic ethers at a concentration of 10% by weight or less.
Polycarbodii prepared from diisocyanate solution
Polycarbodiimide solution containing amide (A) and / or
Is, the formula: 8] (R ₁ represents a lower alkyl group or an alkoxy group)
Carbodiimidation from organic diisocyanate
In the presence of a medium, using a chlorinated aliphatic hydrocarbon as a solvent,
From organic diisocyanate solution with a concentration of 15% by weight or less
Polycarbodiimide containing manufactured polycarbodiimide
A composite comprising a substrate treated with a solution (B) and further heat-treated in an epoxy polymer or a polyester polymer as a matrix resin. 3. The composite according to claim 1, wherein the heat treatment is performed at a temperature of 70 ° C. or higher. 4. The method according to claim 1, wherein the polycarbodiimide solution (A) is an organic solvent.
Tolylene diisocyanate as diisocyanate, 0
- is prepared using tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, or mixtures thereof
The composite according to claim 1, wherein the composite is prepared . 5. The method according to claim 1, wherein the polycarbodiimide solution (B) is an organic solvent.
Use tolylene diisocyanate as diisocyanate
The composite according to claim 1, wherein the composite is produced by using the composite. 6. The alicyclic ether is tetrahydrofuran,
3. The complex according to claim 1, which is dioxane, tetrahydropyran or a mixed solvent thereof. 7. The complex according to claim 1, wherein the chlorinated aliphatic hydrocarbon is tetrachloroethylene, trichloroethylene, or a mixed solvent thereof. 8. The composite according to claim 1, wherein the one substrate is an adherend, a fiber, a filler, or the like. 9. The composite according to claim 2, wherein the substrate is an adherend, a fiber, a filler, or the like. 10. The conjugate substrate is represented by the formula : (In the formula, R ₁ represents a lower alkyl group or a lower alkoxy group.
Represents) or the formula : (Wherein R ₂ and R ₃ represent a hydrogen atom, a lower alkyl group or
Represents a grade alkoxy group), or a formula: 11] (Wherein R ₄ and R ₅ represent a hydrogen atom, a lower alkyl group or a lower alkyl group)
X represents an oxygen atom or a methylene group, respectively.
One or more than the group of organic diisocyanates represented by
The above is selected, and in the presence of a carbodiimidization catalyst,
And use alicyclic ethers at a concentration of 10% by weight or less.
Polycarbodii prepared from diisocyanate solution
Polycarbodiimide solution containing amide (A) and / or
Is, the formula: 12] (R ₁ represents a lower alkyl group or an alkoxy group)
Carbodiimidation from organic diisocyanate
In the presence of a medium, using a chlorinated aliphatic hydrocarbon as a solvent,
From organic diisocyanate solution with a concentration of 15% by weight or less
Polycarbodiimide containing manufactured polycarbodiimide
A method for producing a composite, comprising treating with an epoxy solution or a polyester resin as an adhesive or a matrix resin after treating with a solution (B) and further heat treatment. 11. The method according to claim 10, wherein the heat treatment is performed at a temperature of 70 ° C. or higher. 12. The organic diisocyanate of the polycarbodiimide solution (A), wherein the organic diisocyanate is tolylene diisocyanate, 0-tolidine diisocyanate, 4,4′-diphenylmethane diisocyanate,
2. The product produced using 4,4'-diphenyl ether diisocyanate or a mixture thereof.
0. The method for producing the composite according to 0. 13. The method according to claim 1, wherein the polycarbodiimide solution (B) is
Tolylene diisocyanate as a machine diisocyanate
The method for producing a composite according to claim 10, which is produced by using the composite. 14. The method for producing a composite according to claim 10, wherein the alicyclic ether is tetrahydrofuran, dioxane, tetrahydropyran or a mixed solvent thereof. 15. The method for producing a composite according to claim 10, wherein the chlorinated aliphatic hydrocarbon is tetrachloroethylene, trichloroethylene or a mixed solvent thereof. 16. The method for producing a composite according to claim 12, wherein the substrate is an adherend, a fiber, a filler, or the like.