JPS603325B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diallyl phthalate resin-based solvent-free resin composition.

Conventionally, solution-type resin compositions in which diallylphthalate-based resin compositions are dissolved in organic solvents such as acetone, methyl ethyl ketone, and toluene have been known as resin compositions for iQ-hoko boards. The production of resin-impregnated paper cloth requires a drying process using a solvent and a solvent recovery device, and even after drying, the obtained impregnated paper cloth still contains a few percent of solvent, so the impregnated paper fabric remains sticky. However, this caused problems in storage stability, workability, etc.

On the other hand, as diallyl phthalate-based solvent-free resin compositions, resin compositions with diallyl phthalate prepolymers or unsaturated polyesters using reactive monomers that are liquid at room temperature are known. The resin-impregnated paper fabric obtained in the same way as the solvent-type paper fabric has adhesiveness, and therefore has poor workability during molding, which is a major obstacle to shortening the molding cycle. The present invention provides a diallyl phthalate resin-based solvent-free resin composition that has improved the above-mentioned drawbacks and has an improved resin curing speed.
% by weight, 'b} 5-7% by weight of a substance selected from the group listed below that is solid at room temperature, 'c' 0-65% by weight of an unsaturated polyester that is solid at room temperature, 'd - Reactive monomer that is liquid at room temperature This is a solvent-free resin composition characterized in that it contains 1 to 6 parts by weight of a polymerization initiator per 10 parts by weight of a resin mixture consisting of 0 to 1% by weight.

The diallyl phthalate prepolymer used in the present invention as a component of diallyl phthalate is a prepolymer of diallyl phthalate, which is obtained by polymerizing ortho, iso, and tele monomers and usually has a number average molecular weight of 2,000 to 20,000. Refers to a soluble polymer containing an IJ group.

Component 'b}, which is solid at room temperature, is one selected from the group below, which has excellent compatibility and copolymerizability with the diallyl phthalate prepolymer and unsaturated polyester, and has a melting point in the range of 40 to 15,000. It is two or more substances.

That is, p-phenylstyrene, m-phenylstyrene,
These include p-hexadecylstyrene, crotonic acid, p-cyclohexylphenyl methacrylate, tribromophenyl acrylate, vinyl isophthalate, and allyl stearate.

The unsaturated polyester of component {c} includes polybasic unsaturated acids such as maleic acid, fumaric acid, and itaconic acid, polybasic saturated acids such as phthalic anhydride, L-isophthalic acid, and adipic acid, and ethylene glycol. Those with an acid value of 100 or less and solid at room temperature, especially those with a softening point in the range of 40 to 1500C, are used by dehydration condensation using a polyhydric alcohol such as propylene glycol by a conventional method such as a solvent method or a melting method. It will be done. Reactive monomers for the 'd' component include styrene/divinylbenzene, diallyl phthalate,
Selected from those that are liquid at room temperature, such as diallyl malate.

In the resin composition of the present invention, if the content of the diallyl phthalate prepolymer as component 'a' exceeds 95% by weight, the composition may be melt-coated onto a substrate by a fluidized bed method or a static spraying method. Even when the powder is applied to a base material, the melt viscosity of the composition is so high that it cannot be sufficiently fused and retained on the base material. Also, 3% by weight
If it is less than that, it is not possible to maintain the excellent properties of the cured product of the diallyl phthalate resin, such as abrasion resistance, chemical resistance, gloss, and natural feel. The blending of component 'b', a substance that is solid at room temperature, lowers the melt viscosity of the resin composition, makes it easier to coat the substrate, provides a composition that is not sticky at room temperature, and prevents the curing of the resin. However, if the amount is less than 5% by weight, the above effect cannot be sufficiently obtained. Moreover, if it exceeds 7% by weight, the above-mentioned excellent performance as a diallyl phthalate resin composition will be significantly reduced, which is not preferable. The composition of the invention includes:
Within a range that does not reduce the excellent performance as a diallyl phthalate resin composition, that is, 65% by weight or less.
c} Component unsaturated polyester is added.

In addition, in order to adjust the melt viscosity of the composition,
It is mixed in below. The resin composition of the present invention may optionally contain an internal molding agent, a polymerization inhibitor, a coloring agent, an antiblocking agent, and the like, depending on its use.

As a polymerization initiator, peroxides such as benzoyl peroxide, tert-butyl perbenzoate and dicumyl peroxide are used, but when the temperature of the composition during coating is relatively high, dicumyl peroxide is used. It should be determined by considering the relationship between coating temperature and potability time, such as by using a polymerization initiator having a high temperature decomposition point such as peroxide. The appropriate amount is 1 to 6 parts by weight based on 10 parts by weight of the total resin content. In the practice of the present invention, a high-speed rotating mixer such as a Henschel mixer is convenient for mixing the resin composition, and even if bulk unsaturated polyester is used, it can be made into a fine powder mixture by using the mixer. can.

At this time, the mixing temperature must be maintained at 4.0 or lower to avoid blocking of the compound. The obtained powder formulation does not cause any blocking even during long-term storage at room temperature. In order to coat the resin composition of the present invention on substrates such as paper, cloth, glass cloth, glass non-woven fabric, wood veneer, synthetic resin sheet, etc., the above-mentioned powdery compound is applied to the heated substrate using a fluidized bed method or Mainly used are a powder coating method in which the mixture is fused and maintained by electrostatic spraying, and a melt coating method in which the mixture is heated and melted and applied to a substrate using a suitable coating machine such as a roll coater.

In the case of a powder coating method, the coating temperature is suitably 160°C or lower, and in the case of a melt coating method, a coating temperature of 120°C or lower is suitable.

If the temperature exceeds the above, gelation will progress significantly, which will impede coating, which is not preferable. In the case of the melt coating method, unless the melt viscosity of the resin composition is 1000 poise or less, it is not possible to uniformly apply the desired amount of the composition. If the viscosity exceeds this level, troubles such as cutting of the substrate during coating will occur. Therefore, when using the melt coating method,
It is preferable that component 'b} in the composition is contained in an amount of 3% by weight or more.

The amount of paint deposited on the base material varies depending on the application and required performance, but is usually in the range of 30 to 200% based on the weight of the base material. The prepreg coated with the composition of the present invention shows no stickiness at room temperature, can be stored without using a baser such as polyethylene film, and is easy to handle, making it possible to shorten the molding cycle. It is.

The molding conditions for the obtained prepreg differ slightly depending on the type of polymerization initiator used, but the molding conditions for ordinary diallyl phthalate resins can be applied as they are. The present invention will be explained below with reference to Examples.

Examples 1 to 4, Comparative Examples 1 to 3 Each composition shown in Table 1 was mixed in a Henschel mixer to obtain a powdery blend.

When producing a prepreg by coating the obtained above-mentioned formulation on a base material, a powder coating method using a fluidized bed was used for Example 1 and Comparative Examples 1 and 3, and a powder coating method using a fluidized bed was used for Examples 2, 3, 4 and Comparative Example 2.
For this, we adopted a melt coating method using a hot melt roll coater.

In the powder coating method using a fluidized bed, the above-mentioned powdery compound is placed in an Armstrong Vibrofluidizer to about half its capacity, and the air and vibrator are adjusted appropriately to form a fluidized bed. , and patterned paper (PM-22, manufactured by Okujinsha, 30 x 30 sections) with a weight of 80 yen / finish, 14000 for Example 1 and 12 for Comparative Example 3.
After preheating to 0° C., the prepregs were immersed in a fluidized bed for about 5 seconds to obtain prepregs in which the above-mentioned compound was uniformly fused and maintained on both sides. For Comparative Example 1, powder coating was carried out in the same manner as above except that the temperature of the pattern paper was 16,000, but since the powdered compound was not sufficiently softened, the compound was not applied to the pattern paper. It was not kept in place. Furthermore, after repeating the heating and soaking process five times, the patterned paper deteriorated significantly and no prepreg could be obtained in the end. In the melt coating method, the above powdered formulation is supplied to a hot melt roll coater via an extruder, and coated on both sides of the patterned paper at a coating temperature of 100 pm and a coating speed of 5 w/min. Got prepreg.

The presence or absence of tackiness of the powdered formulation and the obtained prepreg was examined, and the results are shown in Table 1.

Regarding the powdered formulation, the formulation was placed in a 500 Z beaker to a depth of 10 degrees, and after being left in a constant temperature bath at 30 pm for one month, the presence or absence of blocking of the formulation was examined.
Also, regarding prepreg, overlap two sheets of this,
Furthermore, with a load of 100k9' applied on top of that, 30
After being left in a constant temperature bath at qo for one month, the presence or absence of fusion between the prepregs was examined.

Table 1 Notes (1) Chlorine number 57.2, methyl ethyl tonne 50 weight scale solution viscosity 99.0 cp (30°C) (2) Isophthalic acid 1 mol, maleic anhydride 1 mol, ethylene glycol 2.02 mol Buty value 40.0 when dehydrated and condensed by melting method
, one with a softening point of 60°C (3) IDR-20S" manufactured by Osaka Soda Co., Ltd. L4) "Nif.

"Nur VN-3" manufactured by Nihon Rika Co., Ltd. '3 A indicates a powder coating method, and B indicates a melt coating method. Next, each of the obtained prepregs was hot-pressed for 2 minutes at 10k9/m on a particle board with a thickness of 15 ribs via a cushion board and a mirror board using a 170 oo heat press to obtain a decorative board. Performance tests were conducted on each decorative board in accordance with the Japanese Agricultural Standards for special plywood, and the results are shown in Table 2.

Table 2

Claims (1)

[Claims] 1 (a) Diallyl phthalate prepolymer 30-9
5% by weight (b) 5 to 70% by weight of a substance solid at room temperature selected from the following group: p-phenylstyrene, m-phenylstyrene, p-hexadecylstyrene, crotonic acid,
p-cyclohexyl phenyl methacrylate, tribromophenyl acrylate, vinyl isophthalate, allyl stearate (c) Unsaturated polyester that is solid at room temperature 0-65% by weight (d) Reactive monomer that is liquid at room temperature 0-10 weight%
A solvent-free resin composition comprising 1 to 6 parts by weight of a polymerization initiator based on 100 parts by weight of a resin mixture consisting of the above components (a) to (d).