JPS6366216A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain resin composition, by containing a copolymer having carbon- carbon unsaturated bond, benzotriazole compound and manganese salt of an organic acid in specific proportions, having excellent curability and electrical characteristics, etc., as well as improved rust preventing property for copper and an alloy thereof and air-drying property. CONSTITUTION:A resin composition, obtained by containing (A) 100pts.wt. total of (i) 20-80pts.wt. copolymer having carbon-carbon unsaturated bond in the side chain, e.g. 2-hydroxyethyl acrylate, etc., and (ii) 20-80pts.wt. monomer [having carboxyl group when the component (i) has hydroxy group], (B) >=0.01 pts.wt. at least one compound consisting of the group of benzotriazole, 1,2,4- triazole and 1,2,4-triazole derivatives and (C) >=0.01pts.wt. manganese salt of an organic acid and capable of preventing occurrence of green rust in the contact surface with copper and an alloy thereof in curing and improving air-drying property.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a resin composition that has excellent curability and properties of cured products, especially electrical properties, and has improved rust prevention ability and air drying properties for copper and copper alloys. It is related to.

(Prior art) Thermosetting resins generally have excellent mechanical properties, electrical properties, thermal properties, etc. Among them, phenolic resins and epoxy resins have excellent electrical properties and also have excellent mechanical properties. There is no electricity.

It is mainly used in the electronic field.

(Problem to be solved by the invention) However, the biggest drawback of these resins is that they have poor curing properties, so they cannot be used in fields that require curing properties (molding cycles) comparable to thermosetting resins. . Therefore, unsaturated polyester resins have attracted attention as thermosetting resins with excellent curability.

However, although this unsaturated polyester resin does exhibit good curability, when the proportion of styrene is increased in order to improve the electrical properties, the resin becomes hard and brittle, resulting in a decrease in mechanical properties. Conversely, if the proportion of styrene is reduced in order to improve mechanical properties, the superiority of electrical properties will be lost. Furthermore, this unsaturated polyester resin
Due to its structure, it easily absorbs moisture, and there is a concern that its electrical and mechanical properties may deteriorate when it absorbs moisture. The present invention solves these problems and further prevents the formation of rust on the contact surfaces with copper and copper alloys during or after hardening.

This improves air-drying properties.

(Means for Solving the Problems) The present invention provides 80 to 20 parts by weight of a copolymer having a carbon-carbon unsaturated bond in its side chain and 2 parts by weight of a monomer copolymerizable therewith.
0 to 80 parts by weight, totaling 100 parts by weight, benzotriazole, 1,2,4-triazole and 1. The present invention relates to a resin composition containing 0.01 part by weight or more of at least one compound selected from the group consisting of λ4-triazole derivatives and 0.01 part by weight or more of an organic acid manganese salt.

fl! in the present invention! A copolymer having a carbon-carbon unsaturated bond in the l chain is, for example, 1.

(a) A compound represented by the general formula (1) (b; a monomer copolymerizable with the compound (1) and (C1 general formula (
The compound represented by U) (where X is a hydroxyl group, amino group, epoxy group, carboxyl group, incyanate group, acid amide group or acid...ride group, C
It may be bonded to <, Y is a hydroxyl group, an amide group, an epoxy group, a carboxyl group.

Among isocyanate groups, acid amide groups, and acid halide groups, it shows reactivity with X, and may be directly bonded to C without going through Yfl-j:R3.
2, Eta and stone are hydrogen atoms and alkyl groups having 1 to 12 carbon atoms.

or is an aromatic group + R4 and R5 have 1 to 1 carbon atoms
2 is an alkylene group or an aromatic group, and may not be present when X or Y is directly bonded to KC (R3 and Y are the same as X or Y, hydrogen atom, carbon number 1 to 12 alkyl group or aromatic group, & is X or ru is Y
An acid anhydride fund may be formed with an oxygen atom in each of R+~1 rice.

Nitrogen atoms, sulfur atoms, halogen atoms, carboxyl groups and hydroxyl groups may be included. ) using
It can be obtained by polymerizing (a) or (al and (b) to obtain a polymer, and then reacting this polymer with (C).
bl does not necessarily have to be used.

In the above formula,
Hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, methyl itaconate (2-hydroxyethyl), methyl itaconate (2-hydroxypropyl), ethyl itaconate (2- Alkyl (2-hydroxyalkyl) esters of itaconic acid such as hydroxypropyl), methyl maleate (2-hydroxyethyl), methyl maleate (2-hydroxyethyl),
-Hydroxybropyrun, ethyl maleate (2-hydroxybropyrane, ethyl maleate).

#) etc. (7) Alcohols such as alkyl (2-hydroxyalkyl) esters of maleic acid, allyl alcohol, methalyl alcohol, β-alkyl substituted products of these alcohols, hydroxymethy-F+-lyacrylamide, hydroxyethyl Hydroxyalkyl acrylamide such as acrylamide, hydroxyalkyl methacrylamide such as hydroxymethyl methacrylamide, hydroxyethyl methacrylamide, 1-phenyl-2-hydroxypropene-1,1-phenyl-3
Examples include compounds containing an aromatic group such as -hydroxybutyric acid and C-1.

X is an amine 7 group (examples of al include 0-aminostyrene, m-aminostyrene, p-aminostyrene, p-aminostyrene,
-Aminostyrenes such as amino-α-methylstyrene,
0-(aminomethyl)styrene.

0-(aminoethyl)styrene, 1-phenyl-3-7
Aminoalkylstyrenes such as minobentene-1,1-phenyl-5-aminopente 7-1.

Methyl itaconate (2-aminoethyl), Methyl itaconate (2-aminopropyl), Ethyl itaconate (2-
Alkyl (aminoalkyl) esters of itaconic acid such as methyl maleate (2-aminoethyl), methyl maleate (2-aminopropyl), ethyl maleate (2-aminopropyl), etc. Examples include alkyl (aminoalkyl) esters.

Examples of [a) where X is an epoxy group include glycidyl acrylates and methacrylates such as glycidyl acrylate and glycidyl methacrylate.

These β-position alkyl substituents and β-position aromatic substituents.

Itaconic acid glycidyl ester, maleic acid glycidyl ester, and their β-alkyl substituted products.

Examples thereof include aromatic substituted products at the β-position, glycidyl ethers such as allyl glycidyl ether, alkyl-substituted products at the β-position, and aromatic substituted products at the β-position.

Examples of (a) in which X is a carboxyl group include methacrylic acid, acrylic acid, their β-alkyl substituted products,
Unsaturated dibasic acids such as itaconic acid and maleic acid, methyl itaconate, ethyl itaconate.

Monoalkyl itaconate such as propyl itaconate and butyl itaconate, methyl maleate, ethyl maleate,
Monoalkyl maleates such as furovir maleate and butyl maleate cause vignetting.

As an example of fa) where X is an isocyanate group.

Examples include isocyanate methyl acrylate, inocyanate ethyl acrylate, isocyanate methyl methacrylate, and inocyanate ethyl methacrylate.

X is an acid amide group or an acid halide group (examples of al include -COC1, COBr, CONH derived from the compound (a) in which X is a carboxyl group)
Examples include compounds having groups such as 2 and the like.

As an example of Fa) which formed an acid anhydride group with cancer X.

Examples include itaconic anhydride and maleic anhydride.

Examples of the monomer (b) copolymerizable with compound (11) include acrylic esters such as methyl acrylate and ethyl acrylate, and methacrylic esters such as methyl methacrylate and ethyl methacrylate.

Styrene derivatives such as styrene and α-methylstyrene; organic nitriles such as acrylonitrile and methacrylate; vinyl esters of organic acids such as vinyl acetate and vinyl propionate; and vinyl chloride.

Examples include pinyldene chloride.

In the compound (C) represented by the general formula (...), Y is
Among the compounds represented by the general formula (0), compounds having the following groups are used. When X is a hydroxyl group.

Yfd is a carboxyl group, incyanate group or acid/ride group, and when X is an amine group, Y is an epoxy group, carboxyl group, isocyanate group, or acid/ride group, and when X is an epoxy group In, Y is an amine group, a carboxyl group, an incyanate group, an acid amide group or an acid halide group.

When X is a carboxyl group, Y is a hydroxyl group,
It is an amino group or an epoxy group, and when X is an incyanate group, Y is a hydroxyl group.

It can be an amine group, carboxyl group or acid amide group.

When X is an acid amide group, Y is an epoxy group, an isocyanate group, or an acid halide group, and when X is an acid...ride group, Y is a hydroxyl group, an amine group, an epoxy group, or an acid amide group. It is the basis.

Examples of methods for producing copolymers having carbon-carbon unsaturated bonds in their side chains include suspension polymerization, bulk polymerization, and solution polymerization.

There are no particular restrictions.

The composition ratio of the resin composition of the present invention can be varied depending on the purpose of use and the environment, but to give a preferable range, the compound represented by the general formula fil can cause yellowing of the resin liquid, From the viewpoint of transparency and moisture resistance of the cured product, it is preferable to react the compound represented by the general formula fI[) in an amount equal to or more than the equivalent molar amount. In addition, the monomer (b) copolymerizable with the compound represented by the general formula fl) is preferably one that has good compatibility with the compound represented by the general formula m and the compound represented by the general formula (■). It is preferable to select

For example, when hydroxyalkyl methacrylates are selected as the compound represented by the general formula CI+, when styrene or the like having poor compatibility is used as a monomer.

Cloudiness of resin liquid and cured product, mechanical properties of cured product, etc.
It is preferable to suppress the monomer fb)o content to 70% by weight or less of (a), [b) and (C). Roughly speaking, the compound (C) represented by the general formula (■) is the compound f represented by the general formula il+ from the curability of the two compositions and the strength of the cured product.
a) and the monomer fbl copolymerizable with it, total 100
It is preferable to use 20M parts or more based on parts by weight.

The polymerization initiator used in the polymerization of (a) or fa) and fbl is used in general radical polymerization.

azo initiators such as azobisisobutyronitrile, azopiscyclohexanecarbonyl), tcrt-
Examples include peroxides such as butyl hydroperoxide and di-tert-butylperoxide, and there are no particular limitations.

Examples of the polymerization inhibitor include hydroquinone, para-benzoquinone, etc., which are used in general radical polymerization, and are not particularly limited.

Further, in some cases, a chain transfer agent of alkyl mercaptans such as dodecyl mercaptan may be used to adjust the molecular weight of the copolymer.

The reaction of (C) with the polymer obtained by polymerizing (a) or (al and (b)) is carried out by a known method, and there are no particular limitations.

The 1,2,4-triazole and its derivatives in the present invention are represented by the general formula (■) (where R and B are hydrogen or 1d-NH2).

R and R' may be the same or different. ) is a compound represented by 1,2.4-triazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,
2,4-triazole and the like.

Manganese nanthenate is an organic acid manganese salt.

Manganese octenoate and the like are used.

In the resin composition of the present invention, a total of 80 to 20 parts by weight of a copolymer having a carbon-carbon unsaturated bond in the side chain and 20 to 80 parts by weight of a monomer copolymerizable with the copolymer is 10 to 10 parts by weight.
Used in an amount that gives 0 parts by weight.

Benzotriazole per 100 parts by weight.

At least one compound selected from the group consisting of 1.2.4-triazole and 1.2.4-) lyazole derivatives is used in an amount of 0.01 part by weight or more, and an organic acid manganese salt is used in an amount of 0.01 part by weight or more. .

Benzotriazole, 1,2,4-triazole.

This is because if the amount of the 1.2.4-triazole derivative and the organic acid manganese salt is less than 0.01 part by weight, the effect of addition will be small. From the viewpoint of the effect of addition, benzotriazole is preferably added in an amount of 0.01 to 3.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, 1. The 4-triazole or 1,2,4-triazole derivative is preferably 01
01 to 3.0 parts by weight, preferably 0.05 to 3.0 parts by weight
Parts by weight of the organic acid manganese salt are preferably 0.01 to 3.
0 parts by weight, preferably in the range of 0.2 to 1.0 parts by weight.

The resin composition of the present invention contains a plasticizer and a stabilizer.

Curing agent (catalyst), thickener, filler, cross-linking agent, reinforcing material (
Reinforcing material) 9 By adding colorants, lubricants, etc., it can be used as a molding material, paint, adhesive, and various other uses.

(Effects of the Invention) 11. The resin composition of the present invention has excellent curability, and also has the ability to prevent rust against copper and copper alloys such as brass, and the ability to prevent coloring and discoloration thereof. It maintains stability and exhibits excellent air drying properties.

(Example) An example will be explained. Parts are by weight.

Preparation of the composition 151 parts of styrene, 1 part of 2-hydroxymethacrylate
A mixture of 89 parts of n-butyl acrylate, 247 parts of azobisisobutyronitrile, and 2.9 parts of di-tert-butyl peroxide was placed in a four-neck flask equipped with a stirrer and a condenser. The entire amount was dropped over 3 hours into 750 parts of methyl isobutyl ketone heated to 100°C. After the completion of the dropwise addition, the reaction was carried out for 6 hours, and no hydroquinone was added.
．． After adding and mixing 12 parts, 142 parts of maleic anhydride was added.

After reacting for another 3 hours, it was confirmed that the measured acid value (55) almost matched the calculated value (value assuming that only one of the two carboxyl groups of mabiic anhydride reacts; 54). Cooled. While reducing the pressure of this reactant,
After heating to 0 to 100°C to remove the solvent (methyl isobutyl ketone), it was dissolved in styrene to obtain a composition.

(Rust prevention test method) As shown in Figures 1 and 2, silicon steel plate 1 (250
mmX 100wX 0.25++n++) to 50mm
9 width 9 [11111, thickness Z 2
Wrap a double cotton-wrapped wide-angle wire 2 of mm width, and
A simulated coil consisting of 4 layers of kraft paper 3 wound with a thickness of 0.13 m was pre-dried at 110°C for 15 hours, and then cooled to form the coils shown in Table 1 (parts by weight based on 100 parts by weight of the above composition). A resin composition containing benzotriazole, etc. and organic acid manganese salt, etc. was impregnated at 750 mmHH for 30 minutes under reduced pressure, and then the remaining droplets were removed at room temperature for 30 minutes, and then cured at 110° C. for 24 hours. Thereafter, the simulated coil was disassembled, and the degree of rust on the coil surface was determined with the naked eye.

FIG. 2 is a sectional view taken along line a-a in FIG. 1.

(Judgment criteria: ×... Significant onset of front step, △・
...No front step, ○...No front step] (Stability test method) 18. Pour the above resin composition into a φ test scissor tube to a depth of 7 cm, Leave it at room temperature for 7 days and judge the presence or absence of precipitate (judgment criteria: ×...precipitate present, ○...no precipitate) (Air drying test method steel plate (100mu+X40mmX0.25mm1) The air-drying properties were determined from the stickiness after the above resin composition was applied to and left at 110° C. for 1 hour.

(Judgment criteria: ×... Sticky, ○... Curved Table 1 Test results (*The amount of benzotriazole etc. added is all 0.2 parts)
From Table 1, it can be seen that in Nfll and Nα9, no benzotriazole or the like was added, so a foreshortening was observed. This is because Nα2 uses oxalic acid as a rust preventive agent.

The stability is poor, and the anti-corrosion ability is low, resulting in stumbling. Nα3 to 8 use benzotriazole etc. as a rust preventive agent, so they have excellent stability and rust prevention properties, but because they use metal salts (cobalt, lead) other than organic acid manganese salts, they are difficult to air dry. Inferior. Nα1 which is an embodiment of the present invention
A value of 0 to 15 not only shows excellent stability and rust prevention properties, but also has good air drying properties.

[Brief explanation of drawings]

FIG. 1 is a perspective view of a test piece used in the rust prevention ability test. FIG. 2 is a sectional view taken along the line a-a in FIG. 1. Explanation of symbols 1...Silicon steel plate 2...Double cotton-wrapped wide-angle wire 3
...Kraft paper

Claims (1)

[Claims] 1. Copolymer 8 having a carbon-carbon unsaturated bond in the side chain
0 to 20 parts by weight and 20 to 8 monomers copolymerizable with this
0 parts by weight to a total of 100 parts by weight, benzotriazole,
0.01 parts by weight or more of at least one compound selected from the group consisting of 1,2,4-triazole and 1,2,4-triazole derivatives and 0.01 parts by weight of an organic acid manganese salt.
A resin composition containing 0.01 parts by weight or more.