JPS6064846A - Fiber reinforced phenol resin molded shape - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fiber-reinforced phenolic resin molded product that has excellent aesthetic appearance.

Unsaturated polyester resin has been well known as a resin for fiber-reinforced resin moldings, and is used for fishing boats, septic tanks, bathtubs,
Widely used for tanks, silos, pipes, etc. The reason why unsaturated polyester resins are widely used is that they have better workability and moldability than other thermosetting resins, such as phenolic resins, melamine resins, and epoxy resins, in both room-temperature and heat-curing cases. It is by far the best.

However, unsaturated polyester resins have a disadvantage in that they have poor 1ltfPA properties and are difficult to use as building materials, etc., which are often required to have flame retardancy under the Building Standards Act.

On the other hand, phenolic resins have the advantage of being highly flame retardant and emitting less toxic gas than unsaturated polyesters, but because they have poor weather resistance and coloring properties, they discolor in a short period of time, impairing their aesthetic appearance, and Unable to color to the desired tone,
The disadvantage is that the product value is significantly reduced. As a remedy for this drawback, a gel coat resin obtained by adding a coloring agent to unsaturated polyester resin is applied to the mold, cured, and then reinforcing fibers impregnated with phenol resin are laminated on top of it. A so-called gel coat coating, which involves heating and pressure molding, is considered, but unsaturated polyester resin and phenol resin have poor adhesion, and the gel coat layer may not adhere or may peel off with a small impact.

As a result of intensive studies to obtain a fiber-reinforced phenolic resin molded product free from the above-mentioned drawbacks, the inventors of the present invention have discovered that novolac-type vinyl ester resin can be used on top of a fiber-reinforced phenol resin layer, for example as a gel coat layer, or as an unsaturated polyester resin. The present inventors have discovered that the above-mentioned drawbacks can be improved by using the primer as a single layer laminated inside a gel coat layer made of resin, and have completed the present invention.

That is, the present invention provides a fiber-reinforced phenol resin molded product characterized by having a novolac type vinyl ester resin layer on a fiber-reinforced phenol resin layer.

The novolac type vinyl ester resin used in the present invention is
General formula (wherein, R is hydrogen atom, chlorine atom, bromine atom, carbon number 1
~4 alkyl group, n represents 0 or an integer from 1 to 15)
A vinyl ester compound obtained by reacting a novolac type polyepoxide represented by the above with an ethylenically unsaturated monocarboxylic acid salt such as (meth)acrylic acid or crotonic acid, and an ethylenically unsaturated monomer that can be copolymerized with the vinyl ester compound. A vinyl ester resin consisting of the following is blended with a conventionally known curing agent, if necessary a curing accelerator, a curing inhibitor, a coloring agent, a chicken agent, an inorganic filler, a flame retardant, and other additives.

Examples of the novolac type polyepoxide represented by the general formula (1) used here include Epiclon N-730, N-738, N-740, N-manufactured by Dainippon Ink & Chemicals.
-770, N-775 (phenol novolac type polyepoxide), Epiclon N-660, N-665
, N-670, N-673, N-680 (Talesol novolanque type polyepoxide), etc., and ethylenically unsaturated monomers include, for example, styrene, α-methylstyrene, halogenated styrene, etc. aromatic vinyl compounds, (meth)acrylic acid esters, diallyl phthalate monomers, etc., and are usually 20 to 80% by weight, preferably 40 to 60% by weight in the vinyl ester resin.
It is blended in the proportion of

The fiber-reinforced phenolic resin used in the present invention includes formaldehyde, paraformaldehyde, acetaldehyde,
Aldehydes such as furfural and benzaldehyde and phenols such as phenol, cresol, ethylphenol, bromophenol, and chlorophenol in the order of aldehyde/phenols = 0.5/1 to 3
/1, preferably 0.8/1 to 2.5/1, is a known resol-type aqueous solution obtained by methylolation in the presence of an alkali catalyst such as potassium hydroxide, sodium hydroxide, or barium hydroxide. phenolic resin (water content 5 to 50% by weight) and organic acids such as para-toluenesulfonic acid, benzenesulfonic acid, and phenolsulfonic acid;
Inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid; formaldehyde,
Syrup-like or The paste compound is applied to fiber reinforcing materials such as surfacing mats, continuous mats, glass cloaks such as preform cloaks, glass fibers such as glass rovings and glass cloth, carbon fibers, polyamide fibers, and boron fibers. It refers to a product that is impregnated with a moisture content of usually 20 to 60% by weight, is shaped, and is cured at room temperature or by heating while still containing water to become a molded product with a moisture content of 5 to 40% by weight. It is something.

The fiber-reinforced phenolic resin molded product of the present invention can be prepared by applying, for example, an unsaturated polyester resin for gel coat to a mold, curing it, and then applying a novolac type vinyl ester resin for primer to the mold using a brush, roller, etc. 500
g/% and after curing, a fiber-reinforced phenolic resin is laminated or, for example, a novolac type vinyl ester resin for gel coat is usually applied at a concentration of 0.05 to 1. applied to the mold at a thickness of Om, preferably 0.3 to 0.5 th;
After curing, fiber-reinforced phenol resin is laminated and cured by heating.

The unsaturated polyester resin used here is maleic acid,
An unsaturated dibasic carboxylic acid such as fumaric acid or its acid anhydride, optionally a saturated dibasic carboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, adipic acid or its acid anhydride, and ethylene glycol. , propylene glycol, dipropylene glycol, neopentyl glycol, 1゜3-butanediol, alkylene oxide adducts of bisphenol A, and unsaturated polyesters obtained by reaction with polyhydric alcohols such as glycerin, styrene, α-methylstyrene, etc. , a curing agent, if necessary a curing accelerator, a curing inhibitor, a coloring agent, a chicken agent, an inorganic filler,
It contains a flame retardant and other additives, and is preferably an unsaturated polyester resin for gel coating.

The fiber-reinforced phenolic resin molded product of the present invention obtained in this manner has excellent appearance and can be used as interior building materials, exterior building materials, housing equipment, more specifically wall materials, ceiling materials, floor materials,
It can be suitably used in applications that require flame retardancy, such as capsule beds, kotatsu, chairs, mini-stores, and engine rooms of fishing boats.

The present invention will be explained in more detail by showing Examples, Comparative Examples, Reference Examples, and Test Examples below. In addition, all parts and percentages in the examples are based on weight.

Participation Example 1 Epicron N-740 (phenol novolac type polyepoxide manufactured by Dainippon Ink Chemical Industry θsan, epoxy equivalent: 1
80] 180 parts and 86 parts of methacrylic acid were reacted at 80°C in the presence of 0.8 parts of 2-methylimidazole and 0.13 parts of hydroquinone to obtain a vinyl ester compound with an acid value of 5.0. Then, 65 parts of this vinyl ester compound was dissolved in 35 parts of styrene to obtain a novolac type vinyl ester resin (I).

Reference Example 2 204 parts of Epiclon N-670 (Taresol Novolanc type polyepoxide manufactured by Dainippon Ink and Chemicals G11, epoxy equivalent weight 204) and 86 parts of methacrylic acid were mixed in the presence of 069 parts of trimethylamine and 0.9 parts of hydroquinone. C. to obtain a vinyl ester compound with an acid value of 4.2, and then 60 parts of this vinyl ester compound was dissolved in 40 parts of styrene to obtain a novolac type vinyl ester tree 111 (■).

Reference Example 3 64 parts of 42% formalin and 94 parts of phenol were reacted at 80°C for 4 hours in the presence of 3.6 parts of barium hydroxide, then the temperature was lowered to 50°C, and 1 Dehydration was performed for a period of time to obtain a resol type phenol resin (A).

Reference Example 4 107 parts of 42% formalin and 94 parts of phenol,
In the presence of 4.8 parts of potassium hydroxide, the mixture was reacted in the same manner as in Reference Example 3 and dehydrated to obtain a resol type phenol resin (B).

Reference Example 5 164 parts of 42% formalin and 94 parts of phenol,
In the presence of 5.7 parts of sodium hydroxide, the reaction was carried out in the same manner as in Reference Example 3, and the resol type phenol resin (C) was obtained by dehydration.
I got it.

Example 1 Novolac type vinyl ester resin (I) 100 parts, Polyton White) J-18011X (Coloring agent manufactured by Dainippon Ink & Chemicals ■) 10 parts, 6% cobalt naphthenate 0.
3 parts and 1 part of Permec N [55% methyl ethyl ketone peroxide manufactured by NOF ■] were mixed to obtain a novolac type vinyl ester resin for gel coat + a), and 300X
After applying to a box-shaped mold for a 300x100m grave to a thickness of 0.3 mm and curing, resol type phenolic resin (A) was applied.
100 parts, 20 parts of calcined gypsum, Dicerick 102-C [hardening agent for phenolic resin manufactured by Dainippon Ink & Chemicals FL]
A fiber-reinforced phenolic resin for lamination impregnated with 10 parts of laminating syrup to three 450 g/rd glass mats with a glass content of 30% was laminated, and after being left at room temperature for 2 hours, After curing at ℃ for 3 hours, the mold was removed to obtain a fiber-reinforced phenol resin molded product of the present invention. This molded product had excellent flame retardancy and good gel coat adhesion.

Example 2 A fiber-reinforced phenol resin molded product of the present invention was obtained in the same manner as in Example 1, except that the novolac vinyl ester resin JIFF (II) was used instead of the novolac vinyl ester resin (1). This molded product has excellent flame retardancy,
Adhesion of the gel coat was also good.

Example 3 100 parts of Polylite GC-230 (unsaturated polyester resin for gel coat manufactured by Dainippon Ink and Chemicals), part of Polyton White, part of r-tsowxlo, 0.3 part of 6% cobalt naphthenate, and 1 part of Permec N were mixed. to obtain unsaturated polyester resin (bl) for gel coat, 30
It was coated to a thickness of 0.3*** in a box-shaped mold measuring 0x300x100m and cured. On top of that, apply 150 g/M of novolac type vinyl ester resin for primer, consisting of 100 parts of novolac type vinyl ester resin (1), 0.3 part of 6% cobalt naphthenate, and 1 part of Permec N, with a brush.
The coating amount was applied and cured. Next, a laminating syrup consisting of 100 parts of resol-type phenolic resin (B), 20 parts of calcined gypsum, and 10 parts of Dicelink 102-C was added on top of the 450 g/rd glass cape to give a glass content of 30%. The fiber-reinforced phenolic resin for lamination impregnated with the resin was laminated, left at room temperature for 2 hours, cured at 60° C. for 3 hours, and then demolded to obtain the fiber-reinforced phenol resin molded product of the present invention. This molded product had excellent flame retardancy and good gel coat adhesion.

Example 4 A fiber-reinforced phenol resin molded product of the present invention was obtained in the same manner as in Example 3, except that novolac vinyl ester resin (II) was used instead of novolac vinyl ester resin (1). This molded product had excellent flame retardancy and good gel coat adhesion.

Comparative Example 1 Same as Example 1 except that unsaturated polyester resin (bl) for gel coat and resol type phenol resin (C) were used instead of novolanque type vinyl ester resin +a+ for gel coat and resol type phenol resin (A). A fiber-reinforced phenolic resin molded product was obtained for comparison.

Although this molded product had excellent flame retardancy, the adhesiveness of the gel coat was so weak that it easily peeled off when impacted with a mallet.

Comparative Example 2 1 liter of unsaturated polyester resin for gel coat was used instead of novolak type vinyl ester resin fat for gel coat, and Polylite pH-133 (unsaturated polyester resin manufactured by Dainippon Ink & Chemicals @) was used instead of fiber-reinforced phenol resin for lamination. Example except that a fiber-reinforced unsaturated polyester resin for lamination was used, in which three glass mats were impregnated with 450 g/I of a laminating resin consisting of 100 parts of Permec N and 1 part of Permec N so that the glass content was 30%. A fiber-reinforced unsaturated polyester resin molded product for comparison was obtained in the same manner as in Example 1. Although this molded product had good gel coat adhesion, it was inferior in flame retardancy.

Test Example 1 The molded products obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were subjected to an adhesive strength test and an external flammability test. The results are shown in Table 1. The test was conducted as follows.

(1) Adhesive Strength Test A sheet of 570 g/m glass roving cloth was impregnated with the gel coat resin used in Examples 1 and 2 or Comparative Examples 1 and 2 to a glass content of 40%, and cured at room temperature. After impregnating and curing the gel coat resin composition obtained in the above manner or used in Examples 3 to 4 in the same manner, 150 g of the primer resin used in Examples 3 to 4 was applied thereon with a brush. A 25 m wide gel coat resin test piece obtained by coating with a coating amount of /A and curing at room temperature, and Example 1
25 mm obtained by impregnating one glass roving cloth with the resol type phenolic resin or unsaturated polyester resin for lamination used in ~4 or Comparative Examples 1 and 2 to a glass content of 40% and curing at room temperature. Laminate the resin test pieces for lamination of the width in the combinations shown in Table 1 (however, 2
Cellophane tape was used to prevent the entire test piece from adhering except for the 5x50m adhesive area), and was cured at 60°C for 2 hours to obtain a test piece with only one end (25x50 dragon) adhered. Pull both ends in the 18o direction to create a 90°
Increase peel strength.

(2) N flammability test A test piece was cut out from the molded products obtained in Examples 1 to 4 and Comparative Examples 1 to 2, and the test was conducted in accordance with JIS K-1321-1973.

Claims (1)

[Claims] A fiber-reinforced phenol resin molded product, characterized in that it has a novolac type vinyl ester resin layer on fiber-reinforced phenol resin waste.