JPS6035012A - Resin composition - Google Patents

Abstract

PURPOSE:To decrease weight loss during curing and to improve electrical properties, etc., at high temperatures, by adding xylyl (meth)acrylate and/or xylylene di(meth)acrylate to an unsaturated polyester. CONSTITUTION:The purpose resin composition in prepared by mixing (A) 100pts. wt. unsaturated polyester obtained by using a hydroxylalkyl isocyanurate [e.g., bis(2-hydroxyethyl)isocyanurate] as the alcohol component with (B) 3-200pts.wt. xylyl (meth)acrylate and/or xylylene di(meth)acrylate, and (C) 0-100pts.wt. monomer copolymerizable with components A and B (e.g., diethylene glycol dimethacrylate). The resulting resin composition can be used suitably as an insulating coating for electric appliances and devices, an adhesive resin, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition. More specifically, it relates to a 1-odorless or low-odor resin composition that exhibits small weight loss during curing and has excellent electrical properties and heat resistance at high temperatures. Unsaturated polyester resin, which is composed of polymers and polymers, has excellent curability, mechanical properties, and chemical properties, so it can be used for cast products, laminated products, molding materials,
It is widely used in applications such as paint and electrical insulation panels. However, such unsaturated polyester resins are inferior in terms of electrical properties and heat resistance at high temperatures, and
Low-boiling substances such as styrene used as polymerizable monomers evaporate and evaporate during work, polluting the work environment and causing weight loss during curing.

As a result of intensive research to improve these drawbacks, the present inventors have discovered that a resin composition consisting of a specific polymerizable monomer and unsaturated polyester can solve the above problems. This discovery led to the completion of the present invention. Therefore, an object of the present invention is to provide an odorless or low-odor resin composition that exhibits a small weight loss upon curing and has excellent electrical properties, mechanical properties, and heat resistance at high temperatures.

2- That is, the resin composition of the present invention is an unsaturated polyester (4)
, xylyl (meth)acrylate and/or xylylene di(meth)acrylate (B) and (4) and (B)
0 to 200 parts by weight of component 03) and 0 to 200 parts by weight of component 03) per 100 parts by weight of component (5).
It is characterized by containing 100 parts by weight.

The unsaturated polyester (5) used in the present invention has an essential unsaturated dibasic acid as an acid component, a saturated dibasic acid or an aliphatic basic acid as necessary, and an essential polyhydric alcohol as an alcohol component. In addition to what is usually called unsaturated polyester, which is produced using monohydric alcohol if necessary, there are also unsaturated polyesters in which imide groups have been introduced into the molecular skeleton, bisphenol type epoxy resins, phenol novolac triboxylic resins, Epoxy (meth)acrylates obtained from epoxy compounds having one or more epoxy groups in the molecule, such as cresol novolak epoxy resins, and unsaturated-basic acids, such as (meth)acrylic acid, can also be used.

Among these, in the present invention, those derived by necessarily using hydroxyalkylisocyanurates as the alcohol component are particularly preferred from the viewpoint of heat resistance and electrical properties. Examples of the hydroxyalkyl isocyanurates include bis(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)in cyanurate, and tris(hydroxypropyl)isocyanurate.

Examples of xylyl (meth)acrylate and xylylene di(meth)acrylate include xylyl acrylate,
Ortho, meta, xylyl methacrylate, xylylene diacrylate and xylylene dimethacrylate
One or more types of para isomers can be used. The amount used is 100% of unsaturated polyester (A)
3 to 200 parts by weight, preferably 5 to 15 parts by weight
It is 0 parts by weight. If the amount is less than 3 parts by weight, the resulting cured resin composition will not have sufficient heat resistance, and if the amount exceeds 200 parts by weight, the resulting cured product will tend to become brittle.

Unsaturated polyester (4) and xylyl (meth)acrylate and/or xylylene di(meth)acrylate (
6) copolymerizable monomers (Q includes aromatic vinyl compounds, allyl esters, allyl ethers, acrylic esters, methacrylic esters, polyfunctional (
Polymerizable vinyl monomers such as meth)acrylic acid esters and oligo(meth)acrylates can be used, and the amount used is 0 to 100 parts by weight per 100 parts by weight of the unsaturated polyester. If the amount exceeds 100 parts by weight, the weight loss of the resulting resin composition during curing will be large and the heat resistance will be poor.

Curing of the resin composition of the present invention can be carried out using a polymerization initiator commonly used in the art. As a polymerization initiator, acyl peroxides such as benzoyl peroxide and acetyl peroxide; hydroperoxides such as t-butyl peroxide and cumene hydroperoxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; Dialkyl peroxide such as t-butyl peroxide and dicumyl peroxide: t
- Oxyperoxides such as butyl peroxyacetate can be added.

Furthermore, together with these polymerization initiators, organometallic salts such as cobalt octenoate, cobalt naphthenate, iron octenoate, manganese octenoate, and calcium octenoate, and rooting amines such as N, N-dimethylaniline are used as curing accelerators. It is also possible to use them together.

This resin composition can be cured by a method such as room temperature curing, heating furnace curing, infrared curing, or high frequency heating curing. This resin composition also contains benzoin,
It is also possible to add a conventional photosensitizer such as benzophenone and carry out ultraviolet curing. Moreover, it is also possible to use ultraviolet ray curing and heat curing together, and it is also possible to perform electron beam curing.

In addition, additives commonly used in the field of foil technology, such as silicone-based or acrylic leveling agents, thixotropic agents and fillers such as silicic anhydride fine particles, calcium carbonate, crushed stone powder, clay, glass powder, glass fiber, and mica, etc. can also be used effectively.

The thus obtained resin composition of the present invention has a small weight loss upon curing and is odorless or low odor, and the coating film and molded product obtained by curing have excellent electrical properties and heat resistance. Moreover, it is useful as a resin for various paints, inks, adhesives, etc. for coating films, and as a resin for casting, FRP, etc.

Hereinafter, the present invention will be explained in more detail using examples. still,
In the examples, "1 part" refers to "1 part by weight".

Example 1 564 parts of soybean fatty acid, 166 parts of isophthalic acid, 116 parts of fumaric acid, 418 parts of tris(2-hydroxyethyl)in cyanurate, 62 parts of ethylene glycol, and 0.02 part of hydroquinone were placed in a flask equipped with a stirrer, and a nitrogen stream was added. Dehydration condensation was carried out at 160 to 230° C. for 16 hours to obtain unsaturated polyester [11] with an acid value of 24.5.

70 parts of 0-xylylene diacrylate, 20 parts of diethylene glycol dimethacrylate and 0.02 parts of hydroquinone were added to 11,100 parts of this unsaturated polyester (11,100 parts).
A transparent resin composition 111 was obtained by stirring and dissolving at 00°C. Table 1 shows the appearance and odor of the resin composition (1).

100 parts of this resin composition was mixed with 1 part of a curing catalyst (t-butyl peroxybenzoate) and cured at 160°C for 60 minutes.The appearance and electrical properties of the cured coating film obtained (J
The measurement results according to IS C2103) are shown in Table 1. In addition, 1.52% of the resin composition (1) to which a curing catalyst was added
It was spread out on an aluminum curve of 60 diameter and cured at 160° C. for 30 minutes, and the weight loss during curing is shown in Table 1. Next, the weight of the cured coating film obtained in this aluminum 1+11 was set to 100, and the weight loss was measured after being left in a constant temperature bath at 250° C. for 240 hours, and the weight loss is shown in Table 1 as heating loss (4).

In addition, the total weight loss was expressed as (heat loss) based on the weight before curing.

In addition, the adhesive strength of the resin composition (1) to which a curing catalyst was added was 160% by the helical coil method (ASTMD2519).
After curing at ℃ for 60 minutes, the sample was further heated at 250℃ for 240 hours and then measured.

Example 2 35 parts of 0-xylyl methacrylate, 35 parts of O-xylylene dimethacrylate, 20 parts of diethylene glycol dimethacrylate, and 0.02 parts of hydroquinone were added to 11,100 parts of the unsaturated polyester obtained in Example 1 at 100°C. The mixture was stirred and dissolved to obtain a transparent resin composition r21.

This resin composition r2+ was tested in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 70 parts of styrene, 20 parts of diethylene glycol dimethacrylate and 0.02 parts of hydroquinone were added to 11,100 parts of the unsaturated polyester obtained in Example 1 at 100°C.
A transparent resin composition was obtained by stirring and dissolving (hereinafter referred to as comparative resin composition +11).

This comparative resin composition (11) was tested in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 70 parts of sialyl phthalate, 20 parts of diethylene glycol dimethacrylate and 0.02 parts of hydroquinone were added to 111,100 parts of the unsaturated polyester obtained in Example 1.
A transparent resin composition was obtained by stirring and dissolving a portion at 100°C.

(Hereinafter referred to as Comparative Resin Composition (21).)

゛ The comparative resin composition 121K was tested in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 148 f of phthalic anhydride, 982 g of maleic anhydride, and 295 t of dipropylene glycol were placed in a flask equipped with a stirrer, and a dehydration network reaction was carried out at 160 to 240°C for 8 hours under a nitrogen stream to obtain an acid value of 29.0. Unsaturated polyester (3
) was obtained.

To this unsaturated polyester + 31,100 parts, 100 parts of O-xylylene diacrylate and 0.02 parts of hydroquinone.
A transparent resin composition (31) was obtained by stirring and dissolving a portion at 80°C.

This resin composition +31K was tested in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 To 31,100 parts of the unsaturated polyester obtained in Example 3, 50 parts of O-xylylene diacrylate, 50 parts of 0-xylylene dimethacrylate, and 0.
A transparent resin composition (4) was obtained by stirring and dissolving 02 parts at 80°C.
I got it.

This resin composition (4) was tested in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3 100 parts of styrene and 0.02 parts of hydroquinone were added to 8 parts of the unsaturated polyester obtained in Example 3 (31,100 parts).
A transparent resin composition was obtained by stirring and dissolving at 0°C (hereinafter referred to as
Comparative resin composition (referred to as 31).

This comparative resin composition +31 was tested in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 4 To 131,100 parts of the unsaturated polyester obtained in Example 3, 100 parts of diallyl phthalate and 0.0 parts of hydroquinone were added.
02 parts was stirred and dissolved at 80° C. to obtain a transparent resin composition (hereinafter referred to as comparative resin composition (4)).

This comparative resin composition (4) was tested in the same manner as in Example 1, and the results are shown in Table 1.

As is clear from the results shown in Table 1, the resin composition of the present invention has no harmful or unpleasant odor during operation, has small weight loss during curing and heating, and is resistant to electricity at high temperatures. It has excellent physical properties and heat resistance.

Example 5 For 100 parts of each of the resin composition 111 obtained in Example 1 and the comparative resin composition 11 obtained in Comparative Example 1, 0.3 parts of cobalt octenoate and 1 part of methyl ethyl ketone peroxide were added. They were added and mixed, and cured at room temperature to create a casting plate with a thickness of 2 mm.

After curing, it was left in a constant temperature bath at 250°C for 240 hours, and the weight loss was measured.

The cured product of resin composition +11 had a decrease of 11 cI compared to before heating, but that of comparative resin composition (1) had a decrease of 45 cI.
Due to the decrease in I, cracks were generated.

Patent applicant: Nippon Shokubai Chemical Industry Co., Ltd. 14- -1 fishing-

Claims (1)

[Claims] 1. Unsaturated polyester, xylyl (meth)acrylate and/or xylylene di(meth)acrylate) C
B) and (6) and 0 of the monomer copolymerizable with (B), 3 to 20 of component (6) per 100 parts by weight of component (6)
0 parts by weight and (Q component) in a ratio of 0 to 100 parts by weight. 2. The unsaturated polyester (6) is colored with an alcohol component and hydroxyalkyl isocyanurate is used. The resin composition according to claim 1, which is obtained.