JPS6049220B2 - Molding material for buttons - Google Patents

Description

[Detailed description of the invention] The present invention relates to a molding material for buttons.

Specifically, the present invention relates to a molding material for buttons that is low in odor and has excellent storage stability. BACKGROUND ART As one of conventional methods for manufacturing buttons, a method is known in which a radical polymerizable thermosetting resin is cured under heat and pressure.

However, many of the radically polymerizable thermosetting resins currently used have poor storage stability and are prone to gelation during storage. In addition, if the radically polymerizable thermosetting resin contains a polymerizable monomer, the working environment may deteriorate due to the vapor of the polymerizable monomer, and unreacted polymerizability may remain in the final product button. Toxicity due to monomer elution is also a problem. In view of the current situation, the present inventors have
We believe that if buttons can be molded under heat and pressure using an unsaturated polyester that does not contain polymerizable monomers, all of the above-mentioned drawbacks can be solved.As a result of intensive research, we have developed a polyhydric alcohol component with a specific composition and An unsaturated polyester with a viscosity within a specific range derived from a dicarboxylic acid component has excellent storage stability, and the main component is a mixture of a specific amount of filler and curing agent with this unsaturated polyester. It was discovered that the molding material has low odor, excellent curing properties, and properties of cured materials, leading to the completion of the present invention.

Therefore, it is an object of the present invention to provide excellent hardening properties and cured products without deterioration of the working environment due to polymerizable monomer vapor or elution of unreacted polymerizable monomers from the final product button. The object of the present invention is to provide a molding material for buttons having various properties.

Other purposes will become apparent from the description below. That is, the button molding material of the present invention comprises five alcohol components containing 50 mol% or more of the following polyhydric alcohol (a) and an acid component (B) containing 50 mol% or more of the following dicarboxylic acid (b).
The main components are an unsaturated polyester (1), a filler (■), and a curing agent (■) manufactured from , (1) 50 to 30 for 10 parts (■)
It is characterized by a ratio of 0.5 to 5 parts by weight and (■) 0.5 to 5 parts by weight.

Polyhydric alcohol (a): one or more selected from the group consisting of ethylene glycol, diethylene glycol and dipropylene glycol Dicarboxylic acid (b): one selected from the group consisting of maleic acid, maleic anhydride and fumaric acid The unsaturated polyester (1) used in the present invention comprises an alcohol component (4) containing 50 mol% or more of a polyhydric alcohol (a) and a dicarboxylic acid (
b) and an acid component (B) containing 50 mol% or more of
It is within the range of 0 to 5,000 poise.

The polyhydric alcohol (a) is one or more selected from the group consisting of ethylene glycol, diethylene glycol and dipropylene glycol. Polyhydric alcohol (
Examples of compounds used as alcohol components other than a) include propylene glycol, triethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,6-hexanediol, and hydrogenated bisphenol A1. Isophthalic acid ethylene glycol diester-5-sodium sulfonate, 2
- Glycols such as sodium sulfo-1,6-dihydroxypropane; representative examples include these glycols and acetic acid! or oxide compounds such as ethylene oxide, propylene oxide, epichlorohydrin, glycidyl methacrylate, and allyl glycidyl ether. In the present invention, it is necessary that polyhydric alcohol (a) accounts for 50 mol% or more of the three polyhydric alcohol components. A small amount of less than 50 mol % is not preferred because the resulting button molding material will not have a sufficient curing speed and will not have good moldability.

Dicarboxylic acid (b) contained at least 50 mol% in the acid component (B)
is one or more selected from the group consisting of maleic acid, maleic anhydride, and fumaric acid. Dicarboxylic acid (
Examples of compounds used as acid components other than b) include citraconic acid, itaconic acid, halogenated maleic anhydride, phthalic anhydride, phthalic acid, halogenated phthalic anhydride,
Examples include isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, phthalic acid-4-sulfonic acid, succinic acid, sodium sulfosuccinic acid, adipic acid, sebacic acid, and azelaic acid. Ester compounds of these acids with lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol can also be used. In the present invention, it is necessary that 50 mol% or more of the acid component (B) be dicarboxylic acid (b).
A small amount of less than 50 mol % is not preferable because the resulting cured button molding material will not have sufficient strength.

- To obtain the unsaturated polyester (1) from the alcohol component (4) and the acid component (B), methods conventionally known in the unsaturated polyester industry can be used.

Furthermore, the unsaturated polyester obtained in this manner is
Is the end functional group a monovalent alcohol, monovalent acid, or epoxy? It is also possible to use compounds modified with a modifying agent such as a di-group-containing compound or an isocyanate compound. The unsaturated polyester (1) in the present invention must have a viscosity at 25° C. in the range of 2,000 to 5,000 poise as measured by a B-type viscometer.

Therefore, when obtaining the unsaturated polyester (1) from the alcohol component (4) and the acid component (B), the reaction must proceed while measuring the viscosity of the reaction product mixture.
Filler (■) for high viscosity exceeding 5000 poise
It is not preferable because it becomes difficult to mix with the curing agent (■) and the curing agent (■), and when it is molded and cured under heat and pressure, the fluidity is poor and workability is impaired. On the other hand, if the viscosity is lower than 2000 poise, the strength of the cured button will be low, which is also not preferable. Examples of fillers (■) used in the present invention include calcium carbonate, clay, bulb, agarite, mica, silica sand, silica, asbestos, glass flakes, glass beads, hydrated alumina, barium sulfate, or mixtures thereof. etc. can be mentioned.

Inhibitors such as hydroquinone and t-butylcatechol, internal mold release agents such as zinc stearate, magnesium oxide, calcium oxide, etc. may also be used as necessary. Thickeners such as metal alkoxides, glass fibers, organic fibers. A reinforcing agent such as inorganic fiber or a coloring pigment can be used in place of a part of the filler. The filler (■) is used in a ratio ranging from 50 to 30 parts by weight per 10 parts by weight of the unsaturated polyester. A small ratio of less than 5 parts by weight is undesirable because cracks are likely to occur due to curing shrinkage.

On the other hand, if it exceeds 30 parts by weight, the resulting cured product will not have sufficient strength, which is also undesirable. As the accelerator (■), a known polymerization initiator used in curing unsaturated polyester resin under heat and pressure can be used.

Examples include benzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroctoate, t-butylberbenzoate, etc. It is used in a ratio ranging from 0.5 to 5 parts by weight. If the amount is less than 0.5 parts by weight, the curing speed will not be sufficient and the strength of the cured product will also be low.

On the other hand, even if the amount exceeds 5 parts by weight, will it reduce the curing time or increase the strength of the cured product as the amount used increases? This is not desirable because it cannot be seen. Unsaturated polyester (1), filler (■)
In order to obtain the button molding material of the present invention from the unsaturated polyester (1), the filler (■) and the curing agent (■), the unsaturated polyester (1), the filler (■) and the curing agent (■) may be mixed simultaneously. ) and a hardening agent (■), then a filler (■)
may be mixed. Such unsaturated polyester (1
), the filler (■), and the curing agent (■), the method or order of mixing them does not limit the present invention. The thus obtained molding material for buttons according to the present invention has low odor because it does not contain polymerizable monomers, and does not cause deterioration of the working environment or remove unreacted polymerizable monomers from the final button product. It has excellent curing properties and cured material properties without the problem of toxicity due to elution from the body. To cure the button molding material of the present invention, a heat and pressure curing method commonly used in the unsaturated polyester resin industry can be used.

Among them, using a breath molding machine equipped with an appropriate mold, 8
At temperatures ranging from 0 to 200'C, contact pressure ~100k9/
A preferred method is to hold the resin under a pressure of d for about 308' to 3 gin to harden it. The button obtained by curing the button molding material of the present invention can be subjected to processing such as facing, polishing, and drilling, as required.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Note that all parts in the examples represent parts by weight. Example 1 Maleic acid, phthalic acid, ethylene glycol and diethylene glycol in a molar ratio of 0.7:0.3:0, respectively.
．． Mix at a ratio of 8:0.25 and heat for 200 minutes under a nitrogen stream.
The resulting product was subjected to dehydration condensation at 25° C. and the reaction was continued until the viscosity measured with a B-type viscometer reached 3,800 poise at 25° C., and the reaction was continued until the viscosity reached 3,800 poise (hereinafter referred to as polyester (A)).

) was obtained. 10 parts by weight of this polyester (A) were mixed with 10 parts by weight of calcium carbonate, 2 parts of toner, 1 part of zinc stearate, and 2 parts of dicumyl peroxide to obtain a molding material (A).

Molding material (A) 2,000g with a diameter of 30C7n and a depth of 6
When the styrene concentration was measured using a Kitagawa detection tube (for styrene) at a position 10G above the center of the surface of the molding material (a) in a 0 cm open container, the styrene concentration was at the detection limit (4). 1 ppm) or less.

Comparative Example 1 Maleic acid, phthalic acid and propylene glycol were mixed in a molar ratio of 0.5:0.5:1.05, respectively, and condensed in the same manner as in Example 1 to obtain an unsaturated polyester (b) ( Hereinafter, it will simply be referred to as polyester.

) was obtained. Add 0.003 parts of styrene and 0.003 parts of hydroquinone to 6 parts of polyester (b) and mix with stirring.
Unsaturated polyester resin (hereinafter simply referred to as resin).

) was obtained. The resin (mouth) was placed in an open container with the same opening as in Example 1, and the styrene concentration was measured in the same manner as in Example 1, and it was found to be 200 ppm.

5 Example 2 The polyester (A) 20k9 obtained in Example 1 was placed in an oil can, capped, and stored at 40°C to examine storage stability, and it was found to be usable even after 6 months. .

Comparative Example 2θ 20 kg of the resin obtained in Comparative Example 1 was placed in an oil can and the container was stoppered, and the storage stability was examined in the same manner as in Example 2. It turned into a gel in 3 months and became unusable. .

Example 3 The molding material (A) obtained in Example 1 was held under a pressure of 20k9/d for 5 minutes using a button mold heated to 150°C to harden it and form a button (A). Created. The surface hardness of the obtained button (a) was 80 on a Percoll hardness tester (No. 935). Comparative Example 3 Maleic acid, phthalic acid, ethylene glycol, and diethylene glycol in a molar ratio of 0.4:0.6:0, respectively.
．． Unsaturated polyester (c) (hereinafter simply referred to as polyester (c)) was used in the same manner as in Example 1, using a ratio of 8:0.25.

) was obtained. Polyester (c) had a viscosity of 3900 poise as measured with a B-type viscometer at 25 TeC. A molding material (c) was prepared by mixing 1 (4) parts of calcium carbonate, 2 parts of toner, 2 parts of dicumyl peroxide, and 1 part of zinc stearate to 1 part of polyester (c).

This molding material (c) was cured in the same manner as in Example 3 to obtain a button (c). The surface hardness of this button (c) was low, measuring 15 on the Barcol hardness tester (No. 935). Comparative Example 4 Maleic acid, phthalic acid, ethylene glycol, and propylene glycol in a molar ratio of 0.7:0.3:0.4:
Unsaturated polyester (2) (hereinafter simply referred to as polyester (2)) was used in the same manner as in Example 1, using a proportion of 0.6.

) was obtained. A molding material (d) was obtained in exactly the same manner as in Example 1. The molding material (d) was used and hardened in the same manner as in Example 3 to form a button (d), but the surface hardness of this button (d) was still low and was measured by the Barcol hardness tester (NO).
．． 935) was 20. Example 4 Approximately 100 g of the buttons (A) obtained in Example 3 were accurately weighed, placed in a constant temperature bath at 200°C, held for 2 hours, taken out and weighed again, and the loss on heating was measured. There was only a .2% weight loss.

Comparative Example 5 Using the button (c) obtained in Comparative Example 3, the weight loss on heating was measured in the same manner as in Example 4, and a weight loss of 0.4% was observed.

Comparative Example 6 To the resin obtained in Comparative Example 1, 1% of a 55% dimethyl phthalate solution of methyl ethyl ketone peroxide and 0.1% of cobalt octenoate as an accelerator were added to produce buttons from unsaturated polyester resin. After curing in a commonly used centrifugal molding machine, the cured product was cut into a disk shape, then heated to 100° C. and held in one piece for after-curing.

The obtained disk-shaped cured product was faceted to form a button (E).
When the heating loss was measured using this button (E) in the same manner as in Example 4, the weight decreased by 1.5%. Example 5 Approximately 100 g of the button (A) obtained in Example 3 was accurately weighed, boiled for 2 hours in hot water of 1e, dried thoroughly, and the weight change was measured. Weight was decreasing.

Comparative Example 7 The weight change was measured in the same manner as in Example 5 except that the button obtained in Comparative Example 6 was used, and the weight was reduced by 1.5%.

Comparative Example 8 Maleic acid, phthalic acid, ethylene glycol, and diethylene glycol in a molar ratio of 0.7:0.3:0, respectively.
．． Mix at a ratio of 8:0.25 and add 200% under nitrogen stream.
Dehydration condensation is carried out at 25°C, and the reaction is continued until the viscosity measured with a B-type viscometer becomes 1,500 poise at 25°C.
It is called.

) was obtained. This polyester (H) was made into a molding material (H) in exactly the same manner as the molding material (A) was obtained in Example 1, and this was cured in the same manner as in Example 3, resulting in a button. Surface hardness is measured using Barcol hardness tester (NO.93)
5) was 40.

Example 6 Maleic acid, phthalic acid and dipropylene glycol were mixed in a molar ratio of 0.8:0.2:1.05, respectively, and dehydrated and condensed in the same manner as in Example 1 to form B type at 25°C. The reaction was continued until the viscosity measured with a viscometer reached 3,000 poise, and the resulting unsaturated polyester (T) (hereinafter simply referred to as polyester (T)).

). This polyester (G) was made into a molding material (B) in exactly the same manner as in Example 1 to obtain the molding material (A), and this was cured in exactly the same manner as in Example 3 to obtain the button ( The surface hardness of
935) was 80. Example 7 Maleic acid, phthalic acid, ethylene glycol and isophthalic acid ethylene glycol diester-5-sodium sulfonate in a molar ratio of 0.7:0.3:0.8:0, respectively.
．． 25 and dehydrated and condensed in the same manner as in Example 1 until the viscosity measured with a B-type viscometer at 25°C was 3.
The reaction was stopped when the temperature reached 200 poise, and unsaturated polyester (f-) (hereinafter simply referred to as polyester (ch)) was added.
It is called.

Claims (1)

[Scope of Claims] 1 Alcohol component (A) containing 50 mol% or more of the following polyhydric alcohol (a) and the following dicarboxylic acid (b)
An unsaturated polyester (I) which is produced from an acid component (B) containing 0 mol% or more and whose viscosity at 25°C is within the range of 2000 to 5000 poise on a B-type viscometer, a filler (II) and a curing agent ( III) as the main component, (I) 10
(II) 50 to 300 parts by weight and (III
) A molding material for buttons, characterized in that the ratio is 0.5 to 5 parts by weight. Polyhydric alcohol (a): one or more selected from the group consisting of ethylene glycol, diethylene glycol and dipropylene glycol Dicarboxylic acid (b): selected from the group consisting of maleic acid, maleic anhydride and fumaric acid 1 type or 2 or more types