JPH1053669A - Synthetic resin molding material containing glass powder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material useful as artificial marble, etc., excellent in hot water resistance, water vapor resistance and transparent feeling free form whitening, yellowing and swelling caused by hot water, etc., comprising glass powder subjected to specific pretreatment. SOLUTION: This synthetic resin molding material is obtained by blending (A) a synthetic resin such as a methacrylic-based resin, an unsaturated polyester resin, an epoxy resin or an allyl resin with (B) glass powder which is heat- treated at >=100 deg.C and <=its melting point, then washed with running water, etc., and optionally treated with a coupling agent (e.g. γ- methacryloyloxypropyltrimethoxysilane). The material comprises especially preferably 30-200 pts.wt. of the component B based on 100 pts.wt. of the component A. Consequently, the dimensional stability of a molded article can be improved without reducing mechanical strength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a synthetic resin molding material containing glass powder, a method for producing the same, and a synthetic resin molded product. More specifically, the present invention is excellent in hot water resistance and moist heat resistance, and even when exposed to hot water or heated steam for a long period of time, does not cause problems such as whitening, yellowing, swelling, etc. The present invention relates to a synthetic resin molding material containing glass powder, which can provide an excellent molded product, and a method for producing the same, and a methacrylic resin, an unsaturated polyester resin, and an epoxy resin obtained by using the synthetic resin molding material of the present invention. , Various synthetic resin molded products such as allyl resin,
In particular, a methacrylic resin molded product can be effectively used for various applications as artificial marble or the like by utilizing the above excellent properties.

[0002]

2. Description of the Related Art Acrylic resins, particularly methacrylic resins, have been used in a wide range of fields as lighting covers, automobile parts, optical parts such as lenses and prisms, etc. due to their excellent weather resistance and excellent transparency. Further, in recent years, with the expansion of the use of acrylic resin, application development has also been carried out as an interior member of a building material, and for example, acrylic artificial marble has been developed. Acrylic artificial marble is usually cross-linked by mixing an inorganic filler, decorating agent, polymerization initiator, etc. with a cross-linkable highly viscous liquid or paste mainly composed of alkyl methacrylate such as methyl methacrylate or its partial polymer. Methacrylic resin molding material,
It is manufactured by cross-linking and curing, molding and, optionally, further cutting to desired dimensions. Specific uses of the acrylic artificial marble include, for example, the top plate (kitchen counter) of a system kitchen, doors and walls, the top plate of a vanity stand, the waist wall and apron of a unit bath, the bathtub, and the counter of a bay window. And the like. In addition to acrylic resins, molded products obtained by curing thermosetting resin molding materials such as unsaturated polyester resins containing inorganic fillers, epoxy resins, allyl resins, etc. Utilizing it, it is used for various purposes as artificial marble.

In an artificial marble made of a synthetic resin molded article such as a methacrylic resin, an unsaturated polyester resin, or an epoxy resin, for the purpose of obtaining an artificial marble having an excellent transparency, transparency and inorganic filler are used as an inorganic filler. Glass powder having excellent heat resistance is widely used. However, artificial marble containing glass powder does not have sufficient hot water resistance and wet heat resistance, and when exposed to hot water or heated steam, whitening, yellowing, etc. occur, resulting in loss of transparency and poor color tone. In addition, problems such as swelling and poor appearance are likely to occur. On the other hand, in recent years, artificial marbles made of synthetic resins such as methacrylic resins and unsaturated polyester resins have taken advantage of their properties such as economical efficiency and good productivity, such as bathtubs, bathrooms, washbasins, kitchen counters and the like. It has been widely used for applications exposed to hot water or heated steam, and from this point, artificial marble such as methacrylic resin or unsaturated polyester resin containing glass powder is resistant to hot water and moisture. It is required to be excellent in heat property.

The above-mentioned phenomena of whitening, yellowing, and swelling that occur when a molded product obtained from a molding material such as a methacrylic resin or an unsaturated polyester resin containing glass powder is exposed to hot water or high-temperature steam. Due to the alkali metal in the glass composition, an ester bond in a matrix resin such as a methacrylic resin or an unsaturated polyester resin surrounding the glass powder, and a bond between the glass powder and a coupling agent applied to the surface thereof are hydrolyzed. It has been found to be broken down and caused.

[0005] Therefore, in order to solve the above-mentioned problems caused by the glass powder, such as a decrease in hot water resistance, (1) 40 to 60% by weight of SiO ₂ , B ₂ O ₃
10 to 30% by weight, 5 to 20% by weight of alkali metal oxide, 5 to 3 in total of alkaline earth oxide and ZnO
0% by weight and, if necessary, a glass powder having a glass composition having the property of containing other metal oxides. A filler obtained by treating a glass powder with a silane coupling agent or an organopolysiloxane is used as a thermosetting resin such as an unsaturated polyester resin. (2) A specific glass composition having an alkali metal oxide content of 1.0% by weight or less, to form a molded article used as artificial marble or the like by being incorporated therein. Of artificial marble by blending a glass powder having the formula (1) into a thermosetting resin (JP-A-6-13618)
No. 0) has been proposed.

[0006] However, the conventional methods described in (1) and (2) above use glass powder adjusted to a specific glass composition, so that a glass powder having a special glass composition is separately prepared. Therefore, it is necessary to produce the artificial marble-like molded article by incorporating the glass powder into a synthetic resin, and it is not possible to appropriately select and use a conventional general-purpose glass powder. Therefore, it is troublesome, inconvenient, and disadvantageous in terms of cost in that glass powder having a specific glass composition is separately specially prepared.

Moreover, in the case of the conventional methods described in the above (1) and (2), since the glass composition of the glass powder is specially adjusted, the refractive index of the glass powder is large depending on the glass composition. It is regulated to have a specific refractive index, and the refractive index of the glass powder does not always coincide with the refractive index of the synthetic resin material into which the glass powder is to be blended. When the difference between the refractive index of the synthetic resin material and the refractive index of the glass powder is large, even if a transparent glass powder is blended in the synthetic resin material, the difference in the refractive indices of the two provides excellent transparency. A molded article cannot be obtained and cannot be used effectively as artificial marble or the like.

[0008] In fact, in the prior art cited in the above (2), the refractive index of the glass powder having a content of alkali metal oxide of 1% by weight or less and having a specific glass composition is about 1. 53 to 1.58. Then, when this glass powder having a refractive index of about 1.53 to 1.58 is blended with an unsaturated polyester resin having a refractive index of 1.56 to 1.58, the refractive indexes of both are approximated. Therefore, a molded article having a transparent feeling is easily obtained, but when the glass powder having a refractive index of about 1.53 to 1.58 is mixed with the methacrylic resin, the refractive index of the methacrylic resin becomes Since it is generally about 1.48 to 1.52, the difference in the refractive index between the methacrylic resin and the glass powder is large, and a product excellent in transparency cannot be obtained. When the melting temperature is increased during molding of the methacrylic resin in order to obtain a transparent product, phase separation occurs between the methacrylic resin and the glass powder when the molded product is cooled, and as a result, the transparency is excellent. A product cannot be obtained, and other physical properties such as mechanical strength are inferior.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide excellent properties such as hot water resistance and wet heat resistance.
Synthetic resin molding material containing glass powder that does not cause whitening, yellowing, swelling, etc. even when exposed to hot water or heated steam for a long time, especially methacrylic resin containing such glass powder, unsaturated An object of the present invention is to provide a synthetic resin molding material such as a polyester resin, an epoxy resin and an allyl resin, a method for producing the same, and a molded product obtained thereby. And, the object of the present invention is to use a glass powder whose glass composition has been adjusted to a special one without using a glass powder, and appropriately selecting and using an appropriate one from conventional glass powders, An object of the present invention is to provide a synthetic resin molded product that can be effectively used as artificial marble or the like having excellent heat and moisture resistance and transparency, a synthetic resin molding material therefor, and a method for producing the same.

[0010]

The present inventors have studied from various points in order to achieve the above object. The glass powder was blended with a synthetic resin such as methacrylic resin to create a synthetic resin molding material, which was used to produce molded articles used as artificial marble. Then, it was confirmed that the alkali metal component migrated (moved) to the surface of the glass powder. Thus, the present inventors have found that, in the presence of hot water or heated steam, the alkali metal component that has migrated to the surface of the glass powder has a bonding portion between the coupling agent applied to the surface of the glass powder and the glass powder. And accelerated cleavage of ester bonds in synthetic resins. And based on such knowledge, without directly blending the glass powder into the synthetic resin,
The glass powder is heat-treated in advance to positively migrate the alkali metal content contained in the glass powder to the surface, and the alkali metal that has migrated to the surface is removed by washing treatment, followed by heat treatment and washing treatment. A molded article was produced by blending the glass powder subjected to the above-mentioned treatment into a synthetic resin, and the molded article obtained thereby was higher in hot water resistance and moisture resistance than a molded article blended with glass powder not subjected to heat treatment and washing treatment. It has been found that the thermal properties are greatly improved, and no whitening, yellowing, swelling or the like occurs even when exposed to hot water or heated steam for a long time.

In addition, the inventors of the present invention have proposed a method of producing a molded product by mixing a glass powder with a synthetic resin after heat-treating and washing the glass powder. It is not necessary to specially prepare a glass powder having a specific glass composition as in (1) and (2), and among conventionally known glass powders,
What is the same as or approximate to the refractive index of the synthetic resin to be compounded is appropriately selected, and it may be heat-treated and washed to be compounded into each synthetic resin. The present inventors have found that a molded article having excellent transparency can be obtained, and have completed the present invention based on those findings.

That is, the present invention relates to a synthetic resin molding material characterized by containing a glass powder which has been subjected to a heat treatment at a temperature of 100 ° C. or higher, followed by a washing treatment and, if necessary, further treated with a coupling agent. is there. And this invention includes the molded article obtained using said synthetic resin molding material.

Further, according to the present invention, the glass powder is heated to 100 ° C.
A method for producing a synthetic resin molding material characterized by comprising a heat treatment at the above temperature, followed by a washing treatment, a further treatment with a coupling agent as necessary, and a glass powder obtained thereby mixed with the synthetic resin molding material. is there.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, as described above, methacrylic resin,
It is necessary to use a glass powder mixed in a synthetic resin such as an unsaturated polyester resin, an epoxy resin, or an allyl resin that has been heat-treated at a temperature of 100 ° C. or higher and then washed, and heat-treated at a temperature lower than 100 ° C. Even if the glass powder is mixed with the synthetic resin, a molded article with improved hot water resistance and wet heat resistance cannot be obtained. The heat treatment temperature of the glass powder is preferably 130 ° C. or higher, more preferably 150 ° C. or higher. However, the heat treatment temperature must be lower than the melting point of the glass powder, and when heat treatment is performed at a temperature equal to or higher than the melting point of the glass powder, problems such as shape change and aggregation due to melting of the glass powder often occur.

In general, a cleaning treatment is performed after a heat treatment at a temperature between a molding temperature or higher at the time of molding a synthetic resin molding material containing glass powder and a temperature about 100 ° C. higher than the molding temperature. It is preferable to use glass powder, whereby a molded article having further improved hot water resistance and wet heat resistance can be obtained. Although not limited, for example, in the case of a crosslinkable methacrylic resin molding material, a glass powder which has been subjected to a heat treatment at about 100 to 200 ° C. and then washed as a glass powder is preferably used, and in the case of an unsaturated polyester resin, Glass powder that has been heat-treated at about 100 to 200 ° C. and then washed is preferably used. For epoxy resins, glass powder that has been heat-treated at a temperature of about 100 to 150 ° C. and then washed is preferably used.

The time of the heat treatment when the glass powder is heat-treated at 100 ° C. or higher can be adjusted according to the glass composition, particle size, heat treatment temperature and the like of the glass powder.
It is preferably 10 minutes or more and less than 24 hours, and
More preferably, it is time. In general, when the heat treatment temperature is low, the heat treatment is preferably performed for a long time, and the heat treatment time can be shortened as the heat treatment temperature increases. Care should be taken when the heat treatment of the glass powder is performed excessively, because impurities and the like contained in the glass powder may be denatured to cause discoloration of the glass powder.

Next, the alkali metal contained in the glass powder is migrated to the surface of the glass powder by decomposition or the like by the above-mentioned heat treatment, and is removed by a washing treatment. From this point, it is necessary to perform the cleaning treatment sufficiently to substantially remove the alkali metal component that has migrated to the glass powder and possibly other impurities present on the surface of the glass powder. Therefore, the term "cleaning treatment" as used herein means a cleaning treatment in which the migrated alkali metal and other impurities can be substantially removed from the surface of the glass powder. For example, if the alkali metal component or the like migrated by the heat treatment is not sufficiently removed because the cleaning time is too short, etc., it does not correspond to the cleaning treatment in the present invention.

The cleaning treatment is not particularly limited, as long as it can remove alkali metal components sufficiently and does not adversely affect the physical properties of the glass powder after cleaning. The washing treatment can be performed using, for example, water; alcohols such as methanol, ethanol, and isopropyl alcohol; acetone; acids such as hydrochloric acid and sulfuric acid; a mixture of the above-mentioned compounds. This is preferable in that it has a certain point, that the treatment of the washing waste liquid is easy, and that the working environment and the natural environment are not deteriorated because no organic solvent is used. The washing treatment with water is preferably performed under running water. The washing time may vary depending on the amount of glass powder to be subjected to the washing treatment, the amount of the alkali metal that has been migrated, and the amount (flow rate, flow rate) of the washing solution (washing water), but is generally from 1 minute to 24 hours. Wash times of less than are preferably employed.

In the present invention, the glass powder to be mixed with the synthetic resin is subjected to heat treatment and washing treatment.
Those whose alkali metal oxide content is reduced by 10 ppm or more as compared with those before the heat treatment and the cleaning treatment are preferably used, and those whose content is reduced by 15 ppm or more are more preferably used. The content of the alkali metal oxide in the glass powder as referred to in the present specification refers to JIS R 3105 as described in detail in the following Examples.
Means the alkali metal oxide content as measured according to "11.3 Atomic Absorption Method". In addition, the phrase “the alkali metal oxide content of the glass powder is reduced by 10 ppm or more by the heat treatment and the cleaning treatment as compared with before the heat treatment and the cleaning treatment” in the present invention means that the glass before the heat treatment and the cleaning treatment is performed. When the content of the alkali metal oxide in the powder is C _A (ppm) and the content of the alkali metal oxide in the glass powder after the heat treatment and the cleaning treatment is C _B (ppm), the alkali metal oxidation It means that the difference (C _A -C _B ) in the content ratio of the substances is 10 ppm or more.

In the case of using the glass powder which has been subjected to heat treatment and washing treatment, the synthetic resin molded article having excellent hot water resistance and wet heat resistance regardless of the type of the glass powder (particularly the glass composition of the glass powder). Can be obtained smoothly. That is, in the case of the present invention in which the glass powder subjected to the heat treatment and the washing treatment is mixed with the synthetic resin, regardless of the content of the alkali metal oxide in the glass powder before the heat treatment and the washing treatment, Even if a high alkali metal oxide content is used or a low alkali metal oxide content is used), similarly, a synthetic resin molded article excellent in hot water resistance and wet heat resistance is obtained. Can be.

The reason is not clear, but is presumed as follows. That is, when the glass powder is blended with the synthetic resin, the alkali metal component present on the surface portion of the glass powder causes a bond between the glass powder and the coupling agent on the surface thereof in the presence of hot water or heated steam. It mainly acts on the cleavage of ester bonds in the synthetic resin as a matrix surrounding the glass powder, and lowers the hot water resistance and wet heat resistance of the synthetic resin molded article. On the other hand, the alkali metal component present inside the glass powder contained in the synthetic resin does not significantly contribute to the bond with the coupling agent or the cleavage of the ester bond. The alkali metal contained in the glass powder is migrated to the surface of the glass powder due to decomposition or the like during the heat molding when manufacturing a synthetic resin molded product. The alkali metal content at least equivalent to the alkali metal content that is migrated to the glass powder before blending it into the synthetic resin, by previously removing from the glass powder by the above-mentioned heat treatment and washing treatment, such treatment When the glass powder subjected to the above is blended into the synthetic resin, the alkali metal component in the glass powder is no longer migrated to the surface of the glass powder by heating during molding, or is reduced. A decrease in hot water resistance and wet heat resistance of the molded article is prevented. The amount of the alkali metal component that migrates to the surface of the glass powder by heating does not make much difference, even if the content of the alkali metal oxide in the glass powder before the heat treatment and the cleaning treatment is different. Therefore, as described above, the content of the alkali metal oxide is preferably 10 ppm as compared to before the heat treatment and the cleaning treatment.
By using the glass powder subjected to the heat treatment and the washing treatment so as to reduce the above, regardless of the content of the alkali metal oxide in the glass powder before the heat treatment and the washing treatment, the hot water resistance and the moist heat resistance are excellent. It is presumed that a synthetic resin molded product is obtained.

In the present invention, the glass composition of the glass powder is not particularly limited, and an appropriate one can be selected and used according to the kind of the resin in which the glass powder is blended. For example, alkali borosilicate glass, Glass powders composed of alkali silicate glass, soda-lime glass, lead glass, aminosilicate glass and the like can be mentioned. The synthetic resin molding material of the present invention contains one or more of the above-mentioned glass powders. Can be. As described above, when the glass powder that has been subjected to the heat treatment and the cleaning treatment so that the content of the alkali metal oxide is preferably reduced by 10 ppm or more as compared with that before the heat treatment and the washing treatment, the heat treatment and the washing treatment are performed. Regardless of the content of the alkali metal oxide in the previous glass powder, a molded article excellent in hot water resistance and wet heat resistance can be obtained, but if a glass powder having a low alkali metal content is used, a synthetic resin molding can be obtained. The hot water resistance and wet heat resistance of the product are further improved.

In the present invention, a glass powder having a refractive index equal to or close to the refractive index of the synthetic resin in which the glass powder is blended is selected, and the glass powder is subjected to heat treatment and washing treatment. It is possible to obtain a molded product having a better feeling. For example, as the glass powder to be mixed with the methacrylic resin, a glass powder having a refractive index of about 1.48 to 1.52, which is close to the refractive index of the methacrylic resin, is preferably used, and is mixed with the unsaturated polyester resin. As the glass powder, a glass powder having a refractive index of about 1.53 to 1.58, which is close to the refractive index of the unsaturated polyester resin, is preferably used. by the way,
Even if the above-mentioned heat treatment and cleaning treatment at 100 ° C. or higher are performed on the glass powder, the refractive index of the glass powder hardly changes between before and after the treatment. A glass powder suitable for each resin may be selected and used based on the refractive index.

The average particle size of the glass powder is not particularly limited, but is preferably about 2 to 50 μm in that the resulting synthetic resin molded article has good hot water resistance, wet heat resistance, and transparency. If the average particle size of the glass powder is smaller than 2 μm, the specific surface area of the glass powder increases, and the interface with the synthetic resin matrix increases, so that hot water resistance, wet heat resistance, and transparency may decrease. If the average particle size of the powder is larger than 50 μm, the surface of the synthetic resin molded product may have rough surface irregularities, resulting in poor appearance.

In the present invention, the glass powder which has been subjected to the above-mentioned heat treatment and washing treatment may be directly blended into a synthetic resin, or may be further treated with a coupling agent after the above-mentioned heat treatment and washing treatment, and then synthesized. It may be blended in a resin, and is preferably used after being treated with a coupling agent. When the glass powder is treated with a coupling agent and blended into the synthetic resin, a method in which the glass powder after heat treatment and washing treatment is treated with a coupling agent in advance and blended with the synthetic resin, heat treatment Any method may be employed, in which a coupling agent is simultaneously compounded when compounding the washed glass powder into the synthetic resin, or a combination of the above two methods. As the coupling agent at that time, for example, one of silane coupling agents having an unsaturated group, such as γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltris-β-methoxyethoxysilane, or the like; Two or more are preferably used. A synthetic resin molding material is prepared using a glass powder treated with a silane coupling agent after heat treatment and washing treatment, and a molded product is manufactured using the same. Goods can be obtained.

The amount of the glass powder may vary depending on the type of the synthetic resin and the like, but generally, 30 to 200 parts by weight of the glass powder is added to 100 parts by weight of the synthetic resin before the compounding of the glass powder. It is preferable to mix them in proportions,
It is more preferable to mix in a ratio of 80 to 150 parts by weight. In particular, when the synthetic resin is a crosslinkable methacrylic resin, if the blending amount of the glass powder is less than 30 parts by weight with respect to 100 parts by weight of the crosslinkable methacrylic resin, volume shrinkage due to polymerization increases. As a result, the dimensional stability of the molded article tends to be poor, while if it exceeds 200 parts by weight, the mechanical strength of the molded article tends to be reduced.

As the synthetic resin to be mixed with the glass powder subjected to the heat treatment and the washing treatment, as described above, methacrylic resin, unsaturated polyester resin, epoxy resin,
Allyl resin and the like can be mentioned. Among them,
In the present invention, a methacrylic resin is preferably used, and in particular, a crosslinkable methacrylic resin is more preferably used.

Examples of the crosslinkable methacrylic resin preferably used in the present invention include (A) a partially crosslinked alkyl methacrylate gel polymer; (B) an alkyl methacrylate syrup containing an alkyl methacrylate polymer and a crosslinking agent. And (C) a mixture of the partially crosslinked alkyl methacrylate polymer (A) and the alkyl methacrylate syrup (B) described above.

At this time, the partially crosslinked alkyl methacrylate-based gel polymer (A) includes alkyl methacrylate alone; an α, β-ethylenically unsaturated monomer mixture containing alkyl methacrylate as a main component; Polymer raw material selected from alkyl methacrylate syrups in which a methacrylate homopolymer or an alkyl methacrylate copolymer is dissolved in an alkyl methacrylate or in an α, β-ethylenically unsaturated monomer mixture containing alkyl methacrylate as a main component (A ₁ )
A mixture obtained by partially polymerizing and / or crosslinking a mixture containing a crosslinking agent (A ₂ ) is preferably used.

The alkyl methacrylate syrup (B) may be a homopolymer of alkyl methacrylate or a copolymer of an alkyl methacrylate mainly composed of alkyl methacrylate units and another α, β-ethylenically unsaturated monomer. Is mainly α in alkyl methacrylate or alkyl methacrylate,
A syrup mixture of the syrup (B ₁ ) and the crosslinking agent (B ₂ ) dissolved in the β-ethylenically unsaturated monomer mixture is preferably used.

In the above, in the polymer raw material (A ₁ ) and the syrup (B ₁ ), the molar amount of all the monomers used for their preparation (that is, the polymer, the monomer mixture and / or the syrup) Based on the total molar amount of all the monomers used for the formation), it is preferable from the viewpoint of weather resistance that the usage ratio of the alkyl acrylate is 50 mol% or more,
More preferably, it is at least 60 mol%. In this case, as the alkyl methacrylate preferably used,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate,
Examples thereof include butyl methacrylate, and these alkyl methacrylates may be used alone or in combination of two or more. Among them, methyl methacrylate is particularly preferably used.

In the above, when another α, β-ethylenically unsaturated monomer is used together with the alkyl methacrylate for the preparation of the polymer raw material (A ₁ ) and / or the syrup (B ₁ ), , Β-ethylenically unsaturated monomer, whether in the form of a monomer or in the form of a copolymer with an alkyl methacrylate, the other α,
The proportion of the β-ethylenically unsaturated monomer is preferably not more than 50 mol% based on the total molar amount of the alkyl methacrylate and the other α, β-ethylenically unsaturated monomer,
It is preferably at most 40 mol%.

Other α, β-ethylenically unsaturated monomers that can be used in combination with the alkyl methacrylate include, for example, alkyl methacrylates other than the alkyl methacrylate used as the main component (for example, when methyl methacrylate is used as the main component). Is ethyl methacrylate, n
-Propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, etc.); alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate; Hydroxyalkyl (meth) acrylates such as ethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, and 2-hydroxy-3-chloropropyl acrylate; acrylic Acid; methacrylic acid; metal (meth) acrylate Mention may be made of vinyl toluene, maleic anhydride, vinyl chloride, vinyl acetate; Akurironitoniru; acrylamide; styrene, styrene monomers such as α- methylstyrene. Even when only one of these monomers is used in combination with alkyl methacrylate,
Alternatively, two or more kinds may be used in combination with the alkyl methacrylate.

As the polymer raw material (A ₁ ) for forming the partially crosslinked alkyl methacrylate gel polymer (A), an alkyl methacrylate containing an alkyl methacrylate homopolymer or an alkyl methacrylate copolymer is used. When using a system syrup or when using the above-mentioned syrup (B ₁ ), the viscosity is set to 0.1.
It is preferable to use a syrup having a range of 1 to 50 poise and having a content of the alkyl methacrylate homopolymer and / or the alkyl methacrylate copolymer in the syrup of 3 to 70% by weight based on the total weight of the syrup. A syrup having a content of the homopolymer and / or the copolymer of 20 to 45% by weight is more preferably used.

The partially crosslinked alkyl methacrylate gel polymer (A) and / or alkyl methacrylate syrup (B) described above is used for the purpose of improving the impact resistance of the crosslinked alkyl methacrylate polymer molded article. If necessary, an addition polymerization type block copolymer may be contained. As the addition polymerization type block copolymer in this case, an elastomer having rubber properties is preferably used. For example, a polymer block mainly composed of an aromatic vinyl compound unit and a hydrogenated 1,2-bond amount of 30 are used. % Of a polybutadiene block, a hydrogenated polyisoprene block, a hydrogenated polybutadiene block having a 1,2-bond content of 30 to 80%, and a hydrogenated isoprene /
A block copolymer composed of at least one polymer block II selected from the group consisting of butadiene copolymer blocks can be used. When the addition polymerization type block copolymer as described above is used, the amount used is determined by the weight [(A) of the partially crosslinked alkyl methacrylate type gel polymer (A) and / or the alkyl methacrylate type syrup (B)]. (B) when both are used, the total weight is 0.2 to 5% by weight, the effect of improving the impact resistance, the bending of the cross-linked alkyl methacrylate-based polymer molded article, It is preferable from the viewpoint of prevention of whitening and the like.

The crosslinking agent (A ₂ ) used for preparing the partially crosslinked alkyl methacrylate-based gel polymer (A) and the crosslinking agent (B ₂ ) used for preparing the alkyl methacrylate syrup (B) include At least 2
Monomers having two (meth) acryloyl groups are preferably used. More specifically, for example, 1,3-propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, dimethylolethane dimethacrylate,
1,1-dimethylolpropane dimethacrylate, 2,
2-dimethylolpropane dimethacrylate, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanedi (meth) acrylate, ethylene glycol di (meth) acrylate Acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate,
2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypentenoxy) phenyl] propane, 1,4-bis (methacryloyloxymethyl) cyclohexyldi (meth ) Acrylate and the like, and these crosslinking agents can be used alone or in combination of two or more.
Among the above, neopentyl glycol dimethacrylate, 1,4-bis (methacryloyloxymethyl)
Cyclohexyl di (meth) acrylate is preferably used because it can achieve both weather resistance and moldability.

The amount of the crosslinking agent (A ₂ ) to be used is 5 to 10 parts by weight based on 100 parts by weight of the polymer raw material (A ₁ ) used for preparing the partially crosslinked alkyl methacrylate gel polymer (A).
It is preferable that the amount be part by weight, and it is preferable that the amount be 6 to 9 parts by weight. The amount of the crosslinking agent (B ₂ ) to be used is preferably 5 to 10 parts by weight, and more preferably 6 to 9 parts by weight based on 100 parts by weight of the syrup (B ₁ ) used for preparing the alkyl methacrylate syrup (B). It is preferably in parts by weight.

In the partially crosslinked alkyl methacrylate gel polymer (A) and the alkyl methacrylate syrup (B), the content of the linear polymer contained therein is 20 to 40% by weight [partially crosslinked alkyl syrup (B)). When a crosslinked alkyl methacrylate-based polymer molded article is produced using both the methacrylate-based gel polymer (A) and the alkyl methacrylate-based syrup (B), it is preferably based on the total weight of both. More preferably, it is 35% by weight.

The partially crosslinked alkyl methacrylate gel polymer (A) can be produced, for example, by the method described in JP-A-60-202128. That is, a mixture containing the above-mentioned polymer raw material (A ₁ ) and the crosslinking agent (A ₂ ) is added to, for example, a low-temperature active polymerization initiator and heated to a relatively low temperature (generally about 30 to 80 ° C.). By partially polymerizing the polymer raw material (A ₁ ). The type of the low-temperature active polymerization initiator at that time is not particularly limited, and for example, 2,2′-
Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, cumyl peroxy neodecanoate , Diisopropyl peroxydicarbonate, di-n-propylperoxydicarbonate, dimyristyl peroxycarbonate, di- (2-
Ethoxyethyl) peroxydicarbonate, di- (methoxyisopropyl) peroxydicarbonate, di-
(2-ethylhexyl) peroxydicarbonate and the like can be mentioned.

In producing a partially crosslinked alkyl methacrylate gel polymer by partially polymerizing a mixture containing the polymer raw material (A ₁ ) and the crosslinking agent (A ₂ ) in the presence of a polymerization initiator, 4-65% by weight than the polymer content in the mixture of the polymer material to the extent that the polymer content does not exceed 80 wt% (a ₁₎ and the crosslinking agent (a _2), more preferably 10 to Preferably, the partial cross-linking is carried out in such a way that it is increased by 60% by weight, most preferably by 20 to 65% by weight.

In the production of the partially crosslinked alkyl methacrylate-based gel polymer, a low-temperature active polymerization initiator and a high-temperature active polymerization initiator are added to the polymer raw material (A ₁ ). The initiator is activated but heated to a temperature at which the high temperature active polymerization initiator is not activated to form a partially crosslinked alkyl methacrylate gel polymer, and the resulting partially crosslinked alkyl methacrylate gel polymer is obtained. Alternatively, the molded product may be molded at the activation temperature of a high-temperature active polymerization initiator to produce a heat-cured molded product.

When an unsaturated polyester resin is used as the synthetic resin, any of the unsaturated polyester resins conventionally used in the production of artificial marble and the like can be used.
For example, at least one of unsaturated dibasic acids such as maleic anhydride, fumaric acid, and itaconic acid, or anhydrides thereof.
Species; phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
At least one of dibasic acids or anhydrides thereof, such as tetrachlorophthalic anhydride, heptic anhydride, endmethylenetetrahydrophthalic anhydride; and ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, neopentyl Glycol, triethylene glycol, hydrogenated bisphenol A, unsaturated polyester obtained by reacting at least one of polyhydric alcohols such as bisphenol dihydroxypropyl ether with styrene, vinyl toluene, chlorostyrene, phthalate Unsaturated polyester resins obtained by dissolving in vinyl monomers (polymerizable monomers) such as diallyl acid, triallyl cyanurate and methyl methacrylate can be mentioned.

When an epoxy resin is used as the synthetic resin, bisphenol A type epoxy resin, novolak type epoxy resin, brominated epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin and the like can be used.

In order to enhance the design, the synthetic resin molding material of the present invention may contain coloring agents such as dyes and pigments, resin materials, pattern materials such as natural stone particles, and other fillers such as organic short fibers. Other resins of different types can be contained within a range that does not impair the purpose of the present invention.

The method and apparatus for producing the synthetic resin molding material of the present invention containing the heat-treated and washed glass powder are not particularly limited, and any of the methods and apparatuses capable of uniformly mixing the glass powder into the synthetic resin can be used. Can be adopted and can be carried out by employing an appropriate method and apparatus according to the type and content of the synthetic resin, for example, a low-speed kneader such as a double-arm kneader, a high-speed stirrer such as a disper, a screw-type kneader, It can be performed using a kneading roll or the like.

In producing a molded article using the synthetic resin molding material of the present invention containing the heat-treated and washed glass powder, a molding method conventionally used for molding a synthetic resin, particularly a thermosetting resin, is used. Among them, a suitable method may be selected according to the properties of the molding material and the like, and the molding method is not particularly limited. For example, a compression molding method,
It can be molded by employing a casting method, a transfer molding method, an injection molding method, or the like.

Although not limited in any way, for example,
When a molded article is produced using the above partially crosslinked alkyl methacrylate gel polymer (A), a glass powder and a polymerization initiator are added to the partially crosslinked alkyl methacrylate gel polymer (A), and polymerization is initiated. Kneading at a temperature lower than the activation temperature of the agent to prepare a semi-cured molding material,
It is placed in a mold and cured by heating to obtain a crosslinked alkyl methacrylate polymer molded article containing glass powder. When a molded article is produced using both the partially crosslinked alkyl methacrylate gel polymer (A) and the alkyl methacrylate syrup (B), the gel polymer (A), the syrup (B), By mixing a glass powder and a polymerization initiator, mixing or kneading at a temperature lower than the activation temperature of the polymerization initiator to prepare a liquid or semi-cured molding material, placing it in a molding die and heat-curing it. A crosslinked alkyl methacrylate polymer molded article containing glass powder can be obtained.
Further, when a molded article is produced using only the alkyl methacrylate syrup (B) as a polymer raw material, a glass powder and a polymerization initiator are added to the alkyl methacrylate syrup (B) containing the alkyl methacrylate polymer and the crosslinking agent. Are mixed to prepare a liquid or paste-like or solid molding material, which is placed in a molding die and heat-cured to obtain a crosslinked alkyl methacrylate-based polymer molded product.

The shape, structure, dimensions, and the like of the molded article of the present invention containing glass powder are not particularly limited, and can be determined according to the purpose of use or application. Among them, the molded article of the present invention is excellent in hot water resistance, moist heat resistance and transparency, and does not cause whitening, yellowing, swelling and the like even when exposed to hot water and / or heated steam for a long time. Transparency is not lost, and good color tone and appearance with excellent transparency can be maintained.
It can be effectively used as a bathroom wall material, a vanity top plate, a system kitchen top plate, etc.In addition to the above applications, interior materials and equipment for houses such as doors, walls, bay window counters, etc. It can also be used effectively as lumber.

[0049]

EXAMPLES The present invention will be described below in more detail with reference to examples and the like, but the present invention is not limited thereto. In the following examples, the measurement or evaluation of the alkali metal oxide (sodium oxide) content in the glass powder, the light transmittance (transparency) and the hot water resistance of the molded article obtained in each example is as follows. I went.

Alkali metal oxide in glass powder
Measurement of the content of (sodium oxide): The glass powder was dissolved in hydrofluoric acid, and the following equipment was used, under the following measurement conditions, in accordance with JIS R 3105, "11.3 Atomic Absorption Method". The content of alkali metal oxide (sodium oxide) in the glass powder was measured. ○ Equipment used: Atomic absorption spectrophotometer: PerkinElmer “2”
380 type "○ Measurement conditions: Hollow cathode lamp: For Na measurement L233-11NB (current 10 mA) Frame: Air acetylene frame Measurement wavelength: 589 nm Slit width: 0.7 nm

Measurement of light transmittance (transparency) of the molded article:
Length x width x thickness = 50mm x 50mm x 3mm from the molded product
Was cut out, and light was irradiated from the surface direction using a “direct reading haze computer” manufactured by Suga Test Instruments Co., Ltd., and the light transmittance was determined as the total light transmittance. Further, the degree of coloring (yellowing degree) of the test piece was measured by using an SM color computer manufactured by Suga Test Instruments Co., Ltd.
As quantified.

Hot water test of molded article: Test piece cut out of molded article (length × width × thickness = 50 mm × 50)
mm × 3 mm) in a hot water of 90 ± 1 ° C. using a batch type hot water tester (a constant temperature water tank manufactured by Isuzu Seisakusho).
After soaking for 0 hours, the test piece was taken out of the hot water, the light transmittance of the test piece was measured in the same manner as described above, and the degree of coloring (yellowing degree) was measured in the same manner as above. It was quantified as E (degree of yellowing), the degree of whitening and yellowing was examined, and the hot water resistance was evaluated. In addition,
The decrease in light transmittance after the hot water test is 10% or less, and
When the value of E is 8 or less, the degree of whitening and yellowing is small, and there is no practical problem.

Reference Example 1 [Treatment of Glass Powder] (1) An alkali borosilicate glass powder having an alkali metal oxide (sodium oxide content) of 345 ppm as measured by the above-mentioned atomic absorption method (average particle size: 20 μm, After a heat treatment at 150 ° C. for 5 hours, the film was washed with running water for 10 minutes and then dried at 80 ° C. for 2 hours.
The alkali metal oxide content (sodium oxide content) of the glass powder thus obtained was 330 ppm,
By this heat treatment and washing treatment, the content of alkali metal oxide (sodium oxide) in the glass powder is reduced to 15%.
ppm was reduced. (2) A silane coupling agent (γ-methacryloxypropyltrimethoxysilane; “A-174” manufactured by Nihon Unica) is added to 100 parts by weight of the glass powder obtained in the above (1).
Was added and uniformly mixed and subjected to a surface treatment to obtain a glass powder treated with a silane coupling agent.

Reference Example 2 [Treatment of Glass Powder] The same glass powder as used in (1) of Reference Example 1 was used, except that the heat treatment temperature was set to 200 ° C. And the same treatment as in (2) was carried out to obtain a glass powder treated with a silane coupling agent, in which the content of alkali metal oxide (sodium oxide) was reduced by 23 ppm as compared to before the heat treatment and the washing treatment. .

Reference Example 3 [Treatment of Glass Powder] The same glass powder used in (1) of Reference Example 1 was used except that the heat treatment time was 15 hours and the cleaning time was 13 hours. The same treatment as in (1) and (2) of Reference Example 1 was performed, and the content of the alkali metal oxide (sodium oxide) was 17 ppm as compared with before the heat treatment and the cleaning treatment.
A reduced glass powder treated with a silane coupling agent was obtained.

Reference Example 4 [Treatment of Glass Powder] Using the same glass powder as used in (1) of Reference Example 1 and without performing heat treatment and cleaning treatment, the treatment of (2) of Reference Example 1 was carried out. Treated with a silane coupling agent in the same manner as
A glass powder treated with a silane coupling agent was obtained.

Reference Example 5 [Treatment of Glass Powder] The same glass powder as used in (1) of Reference Example 1 was used, except that the heat treatment temperature was set to 60 ° C.
And alkali metal oxide (sodium oxide) compared with before heat treatment and cleaning treatment
A glass powder treated with a silane coupling agent and having a reduced content of 8 ppm was obtained.

Reference Example 6 [Treatment of Glass Powder] The same glass powder used in (1) of Reference Example 1 was used, except that the heat treatment time was changed to 5 minutes. And the same treatment as in (2) was performed to obtain a glass powder treated with a silane coupling agent having a content of alkali metal oxide (sodium oxide) reduced by 5 ppm as compared with before the heat treatment and the washing treatment. .

Reference Example 7 [Treatment of Glass Powder] The same glass powder as used in (1) of Reference Example 1 was used, except that the cleaning treatment time was 0.5 minutes. By performing the same treatment as in (1) and (2), a glass powder treated with a silane coupling agent was obtained in which the content of alkali metal oxide (sodium oxide) was reduced by 3 ppm compared to the heat treatment.

Example 1 (1) A linear polymethyl methacrylate having a viscosity average degree of polymerization of 1300 [HR beads manufactured by Kuraray Co., Ltd.] was 34.7.
860 g of methyl methacrylate syrup containing by weight
And 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) in 1000 g of a polymerizable mixed liquid consisting of 140 g of “NK Ecitel NPG-DM” manufactured by Shin-Nakamura Chemical Co., Ltd.
(Polymerization initiator) 0.045 g and 1,4 (8) -p-
Add and mix 0.07 g of mentadiene (polymerization regulator),
This mixture was poured into a pre-assembled glass cell having an interlayer of 10 mm and sealed with nitrogen. Then, the glass cell was put into a hot water bath at a water temperature of 60 ° C., and polymerization was carried out for 1 hour. A methacrylate gel polymer was obtained.

(2) 1,1 is added to 75 g of the partially crosslinked alkyl methacrylate gel polymer obtained in the above (1).
0.49 g of -bis (t-butylperoxy) -3,3,5-trimethylcyclohexane [“Trigonox 29-N75” manufactured by Kayaku Aguso Co., Ltd.], 2,2-bis- (t
-Butylperoxy) butane [Trigonox DT50 manufactured by Kayaku Aguso Co., Ltd.] 0.06 gg, t-butylperoxyisopropyl carbonate [Kayacarbon BIC-75 manufactured by Kayaku Aguso Co., Ltd.] 0.41 g ,
1,3-Bis (t-butylperoxyisopropyl) benzene [“PARCADOX 14” manufactured by Kayaku Aguso Co., Ltd.]
0.29 g and 75 g of each of the glass powders obtained in Reference Examples 1 to 7 were added, and the mixture was charged into a stirrer / mixer (“Laboplast Mill 30C150” manufactured by Toyo Seiki Co., Ltd.).
The mixture was stirred and mixed at 0 rpm for 10 minutes to prepare a methacrylic resin molding material.

(3) 100 g of the methacrylic resin molding material obtained in the above (2) was previously heated to 130 ° C., and a mold for a flat formed article [mold cavity volume = 150 mm × 150]
mm × 3 mm), and after holding for 10 minutes at a molding pressure of 100 kg / cm ² with respect to the projected area of the molded product,
After cooling to 90 ° C., the mold was opened and the molded product was taken out. (4) 50 mm x 5 from the molded product obtained in (3) above
A test piece of 0 mm × 3 mm was cut out and its light transmittance and its coloring degree (yellowing degree) were measured by the above-mentioned method, and the results were as shown in Table 1 below. (5) Further, when the hot water resistance test was carried out by the above-mentioned method using the test piece of the above (4), the light transmittance of the test piece after the hot water resistance test, the reduced value of the light transmittance, and ΔE
Was as shown in Table 1 below.

[0063]

[Table 1]

From the results shown in Table 1 above, Reference Examples 1, 2, 3, and 5 in which the alkali metal and the like migrated to the surface of the glass powder were removed by heat treatment followed by cleaning treatment.
Or when the crosslinkable methacrylic resin molding materials of Experiment Nos. 1 to 3 and Experiment Nos. 5 to 6 containing the glass powder of No. 6 are used, the obtained molded product has good hot water resistance and can be used for a long time with hot water. It can be seen that even when exposed, whitening or yellowing hardly occurs or the degree thereof is low. Table 1 above
From the results of Experiment Nos. 1 to 3 containing the glass powders of Reference Examples 1 to 3 in which the heat treatment and the cleaning treatment were performed such that the content of the alkali metal oxide was reduced by 10 ppm or more as compared with before the heat treatment and the washing treatment. When the crosslinkable methacrylic resin molding material of No. 3 is used, the molded product obtained therefrom has extremely excellent hot water resistance, and almost no whitening or yellowing occurs even when exposed to hot water for a long time. Recognize.

On the other hand, Experiment No. 4 containing the glass powder of Reference Example 4 which had not been subjected to the heat treatment and the cleaning treatment.
When using a crosslinkable methacrylic resin molding material of
The hot water resistance of the obtained molded product is inferior, whitening and yellowing occur when exposed to hot water, and the transparency is greatly lost,
It can be seen that the color tone is also poor. Furthermore, although the heat treatment and the cleaning treatment of the glass powder are performed, the time of the cleaning treatment after the heat treatment is too short, and the removal of the alkali metal that has migrated to the surface of the glass powder by the heat treatment is substantially performed. When the crosslinkable methacrylic resin molding material of Experiment No. 7 containing the glass powder of Reference Example 7 was not used, the hot water resistance of the obtained molded product was inferior,
It can be seen that when exposed to hot water, whitening and yellowing occur, resulting in a significant loss of transparency and poor color tone.

[0066]

According to the present invention, a synthetic resin molding material is produced by blending glass powder which has been subjected to a heat treatment at a temperature of 100 ° C. or higher and then subjected to a cleaning treatment into a methacrylic resin or other synthetic resin. The hot water resistance and wet heat resistance of the molded product obtained from the synthetic resin molding material are improved, and even if the molded product is exposed to hot water or heated steam for a long period of time, whitening, yellowing, blistering, etc. do not occur, and good transparency and Appearance can be maintained. Therefore, such molded articles of the present invention can be used as artificial marbles, such as bathtubs, bathroom wall materials, top plates for system kitchens (kitchen counters), and top plates for vanity tables, utilizing the above-described excellent properties. It can be effectively used for applications requiring high hot water resistance and wet heat resistance, such as doors and walls, and other interior materials for houses.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08K 9:04 C08L 33:12

Claims (7)

[Claims] 1. A synthetic resin molding material comprising a glass powder which is subjected to a heat treatment at a temperature of 100 ° C. or higher, followed by a washing treatment and, if necessary, further treated with a coupling agent. 2. The synthetic resin molding material according to claim 1, wherein a glass powder whose content of an alkali metal oxide is reduced by 10 ppm or more by heat treatment and washing treatment as compared with before the heat treatment and washing treatment is used. 3. A synthetic resin molding material comprising: (A) a partially crosslinked alkyl methacrylate gel polymer; (B) an alkyl methacrylate syrup containing an alkyl methacrylate polymer and a crosslinking agent; The synthetic resin molding material according to claim 1 or 2, which is a crosslinkable methacrylic resin molding material selected from a mixture of a crosslinked alkyl methacrylate polymer (A) and an alkyl methacrylate syrup (B). 4. The method according to claim 1, wherein the glass powder is subjected to a heat treatment at a temperature of 100 ° C. or higher, followed by a washing treatment, and if necessary, further treatment with a coupling agent, and the resulting glass powder is blended into a synthetic resin molding material. A method for producing a synthetic resin molding material. 5. The method according to claim 4, wherein the heat treatment and the cleaning treatment are performed such that the alkali metal oxide content of the glass powder is reduced by 10 ppm or more as compared with that before the heat treatment and the cleaning treatment. 6. A synthetic resin molding material comprising: (A) a partially crosslinked alkyl methacrylate gel polymer; (B) an alkyl methacrylate syrup containing an alkyl methacrylate polymer and a crosslinking agent; The production method according to claim 4 or 5, which is a crosslinkable methacrylic resin molding material selected from a mixture of a crosslinked alkyl methacrylate polymer (A) and an alkyl methacrylate syrup (B). 7. A synthetic resin molded product obtained by using the synthetic resin molding material according to claim 1.