JP5131956B2 - Thickener and method for producing the same - Google Patents

Description

  The present invention relates to a thickener for syrup in which the manufacturing cost is reduced while maintaining the mechanical strength and durability of conventional artificial marble.

  In general, artificial marble is obtained by heating and polymerizing silica or aluminum hydroxide to syrup. As syrup, a solution of methacrylic resin in methyl methacrylate is used. The methacrylic resin is dissolved as a thickener that increases the viscosity of syrup and facilitates handling. Since the thickening effect is higher as the molecular weight of the methacrylic resin is higher, a solvent-resistant methacrylic resin grade having a high molecular weight of about 150,000 to 200,000 is often employed. However, since the methacrylic resin is not easily dissolved in methyl methacrylate, it is dissolved over several hours while applying heat. For this reason, the production time of the artificial marble is increased, which increases the manufacturing cost. A syrup having a low production cost is desired while maintaining the heat resistance and mechanical strength of conventional artificial marble.

  As a known method for improving the mechanical strength and moldability of a methacrylic resin, there is known a method of imparting fluidity with a low molecular weight methacrylic resin and imparting mechanical strength with a high molecular weight or a micro-crosslinked structure. Since the dissolution characteristics are considered to be better as the moldability is higher, the moldability was set as an item having the same tendency as the dissolution characteristics. (For example, see Patent Documents 1, 2, and 3).

Since the methacrylic resin described in Patent Document 1 has a low molecular weight, the syrup viscosity is low. To adjust the syrup viscosity, it is necessary to increase the amount of methacrylic resin, which is not preferable. Further, the methacrylic resin described in Patent Document 2 can be copolymerized with the methyl methacrylate of the polymer (2) so that the composition ratio of the other vinyl monomer copolymerizable with the methyl methacrylate of the polymer (1) can be copolymerized. More than the composition ratio of other vinyl monomers. When the composition ratio of the other vinyl monomer copolymerizable with methyl methacrylate of the polymer (2) is small, it is expected that the dissolution characteristics are lowered, which is not preferable. The methacrylic resin described in Patent Document 3 is a patent relating to the appearance improvement of a premix produced by adding a methacrylic resin to syrup, and is not a patent relating to a thickener for syrup. Further, methacrylic resin dissolved in syrup is not preferable because it is a one-stage polymerized product and has a wide molecular weight distribution.
JP-A-1-22865 JP 2004-339442 A JP-A-9-111085

  The subject of this invention is providing the thickener of syrup which consists of a methacryl resin which is easy to melt | dissolve in methyl methacrylate and can provide predetermined | prescribed viscosity to syrup.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, found a thickener and a method for producing the same that reduce the production cost while maintaining the mechanical strength and durability of conventional artificial marble.

  That is, the first of the present invention is a methacrylic resin containing 99 to 80 wt% of methyl methacrylate monomer units and 1 to 20 wt% of other vinyl monomer units copolymerizable with at least one methyl methacrylate. The weight average molecular weight of the methacrylic resin measured by gel permeation chromatography (GPC) is 100,000 to 400,000, and the weight is 1/5 or less of the peak weight average molecular weight (Mp) obtained from the GPC elution curve. It is a thickener comprising a methacrylic resin having an average molecular weight component of 8 to 30% based on the methacrylic resin component.

  The second of the present invention is a methacrylic resin having an average particle diameter of 0.05 to 0.5 mm, and the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC). It consists of a methacryl resin which is the relationship of Formula (1), It is said 1st thickener characterized by the above-mentioned. Mw / Mn ≧ 2.3 (1)

In the third aspect of the present invention, another vinyl unit copolymerizable with methyl methacrylate in a methacrylic resin having a weight average molecular weight component having a cumulative area (%) in the GPC elution curve of the methacrylic resin of 0 to 2%. Other vinyl monomers copolymerizable with methyl methacrylate in a methacrylic resin having a weight average molecular weight component having an average composition ratio Mh (wt%) of the monomer unit and a cumulative area area (%) of 98 to 100% The thickener according to the first or second aspect, wherein the average composition ratio Ml (wt%) of the unit is made of a methacrylic resin having the relationship of the formula (2).
(Mh−0.8) ≧ Ml ≧ 0 (2)

  A fourth aspect of the present invention is a method for producing a thickener comprising the methacrylic resin according to the first aspect, and first, 70 to 100 wt% of a methyl methacrylate monomer and another vinyl monomer copolymerizable with methyl methacrylate. Polymer (1) having a weight average weight of 10,000 to 50,000 measured by gel permeation chromatography after polymerizing 30 to 0 wt% of the polymer is 7 to 30 wt% based on the entire methacrylic resin. Then, the polymerization is continued in the presence of the polymer (1), and the polymer (2) having a weight average molecular weight of 110,000 to 600,000 is 93 to 70 wt% based on the entire methacrylic resin. It is a method for producing a thickener comprising a methacrylic resin, characterized by being polymerized so that

  According to a fifth aspect of the present invention, the methacrylic resin is composed of a methacrylic resin having a weight average molecular weight of 100,000 to 400,000 and an average particle diameter of 0.05 to 0.5 mm. It is a manufacturing method of the thickener of description.

The sixth aspect of the present invention is copolymerizable with the composition ratio Mal (wt%) of another vinyl monomer copolymerizable with the methyl methacrylate of the polymer (1) and the methyl methacrylate of the polymer (2). The composition ratio Mah (wt%) of other vinyl monomer units is made of a methacrylic resin having the relationship of the formula (3). is there.
(Mah-0.8) ≧ Mal ≧ 0 (3)

  The thickener according to the present invention has excellent solubility in methyl methacrylate while maintaining the mechanical strength and durability of conventional artificial marble, and can produce syrup in a short time, improving syrup productivity. can do.

  Hereinafter, the present invention will be described in detail. The methacrylic resin which is a thickener of syrup in the present invention is at least one of methyl methacrylate monomer and / or other vinyl monomer copolymerizable with methyl methacrylate monomer and methyl methacrylate. Composed.

The content of methyl methacrylate in the methacrylic resin is preferably 99 to 80 wt%. If it is more than 99 wt%, the heat resistance is unnecessarily improved and the dissolution properties are deteriorated, which is not preferable. On the other hand, if it is less than 80 wt%, the mechanical strength decreases, which is not preferable. Preferably, 99 to 85 wt% is preferable from the viewpoint of heat resistance and dissolution characteristics. More preferably, it is 93-90 wt%.
As other vinyl monomers copolymerizable with methyl methacrylate,
Alkyl methacrylate having 2 to 18 carbon atoms in the alkyl group, alkyl acrylate having 1 to 18 carbon atoms in the alkyl group;
Α, β-unsaturated acids such as acrylic acid and methacrylic acid, unsaturated group-containing divalent carboxylic acids such as maleic acid, fumaric acid and itaconic acid, and alkyl esters thereof;
Aromatic vinyl compounds such as styrene, α-methylstyrene, styrene having a substituent on the benzene ring;
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Maleic anhydride, maleimide, N-substituted maleimide and the like;
Ethylene glycol such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, etc. Esterified;
What esterified the hydroxyl group of two alcohols, such as neopentylglycol di (meth) acrylate and di (meth) acrylate, with acrylic acid or methacrylic acid;
Esterification of polyhydric alcohol derivatives such as trimethylolpropane and pentaerythritol with acrylic acid or methacrylic acid;
Polyfunctional monomers such as divinylbenzene;
These may be used alone or in combination of two or more. Among these, from the viewpoint of light resistance, thermal stability, heat resistance, and fluidity, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, 2-acrylic acid 2- Ethylhexyl and the like are preferably used. Methyl acrylate, ethyl acrylate, and n-butyl acrylate are particularly preferred, and methyl acrylate is most preferred because it is readily available.

  Other vinyl monomers that are copolymerizable with methyl methacrylate affect the dissolution properties and heat resistance. The content is 1 to 20 wt% with respect to the methacrylic resin. From the viewpoint of dissolution characteristics, 1 wt% or more is preferable. Moreover, 20% or less is preferable from the viewpoint of mechanical strength. More preferably, it is 1-15 wt%. More preferably, it is 3-10 wt%.

  As for the methacryl resin which is a thickener of this invention, the weight average molecular weights measured by gel permeation chromatography (GPC) have preferable 100,000-400000. From the viewpoint of the mechanical strength of artificial marble and the amount of resin used, 100,000 or more is preferable. If it is 100,000 or less, the amount of methacrylic resin used is increased to increase the viscosity of syrup, which is not preferable. Moreover, 400000 or less is preferable from a viewpoint of the stable production of superposition | polymerization. More preferably, it is 150,000 to 300,000.

  As for the methacrylic resin which is a thickener of this invention, it is preferable that the weight average molecular weight Mw and number average molecular weight Mn which measured by gel permeation chromatography (GPC) satisfy | fill Formula (1). This is because the larger the Mw / Mn value, the wider the molecular weight distribution, which is advantageous for achieving both mechanical strength and solubility characteristics. More preferably, it is 3 or more. More preferably, it is 5 or more.

Mw / Mn ≧ 2.3 (1)
The weight average molecular weight measured in the present invention is measured by GPC. A standard curve is prepared in advance from the elution time and the weight average molecular weight using a standard methacrylic resin available as a reagent having a known monodispersed weight average molecular weight and an analytical gel column eluted from a high molecular weight component. The molecular weight of each sample can be measured from the calibration curve.

  In the present invention, the peak weight average molecular weight (Mp) refers to the weight average molecular weight showing a peak in the GPC elution curve. When there are a plurality of peaks in the GPC elution curve, the peak is indicated by the weight-average molecular weight having the largest abundance.

  The component having a weight average molecular weight of 1/5 or less of the peak weight average molecular weight present in the methacrylic resin which is the thickener of the present invention is important with respect to the strength and solubility characteristics of the resin. A weight average molecular weight component of 1/5 or less has a plasticizing effect. When the abundance of this component is in the range of 8 to 30% with respect to the methacrylic resin component, the effect of improving the dissolution characteristics is exhibited. From the viewpoint of solubility, it is 8% or more. On the other hand, it is 30% or less from the viewpoint of heat resistance, mechanical strength, cracks and warpage in environmental tests. More preferably, it is 10-25 wt%.

  When the composition ratio in the high molecular weight component of the methacrylic resin obtained is copolymerizable with the methyl methacrylate monomer in the present invention is larger than the composition ratio in the low molecular weight component, It is preferable because the melting characteristics can be further improved while maintaining reliability and mechanical strength such as cracks and warpage in environmental tests.

  Here, the area area in the GPC elution curve indicates the hatched portion shown in FIG. The specific method is as follows. First, the point A at which the baseline 2 automatically drawn by the measuring instrument and the GPC elution curve 1 intersect the GPC elution curve 1 obtained from the elution time obtained by the GPC measurement and the detection intensity by the RI (differential refraction detector). And point B is determined. Point A is a point where the GPC elution curve at the beginning of the elution time and the baseline intersect. Point B is a position where, as a general rule, the weight average molecular weight is 500 or more and the baseline and the GPC elution curve intersect. If the weight average molecular weight does not intersect within the range of 500 or more, the RI detection intensity value at the elution time when the weight average molecular weight is 500 is defined as point B. A hatched portion surrounded by the GPC elution curve between the points A and B and the line segment AB is an area in the GPC elution curve. This area is the area of the GPC elution curve. In this application, since a column eluted from a high molecular weight component is used, a high molecular weight component is observed at the beginning of the elution time, and a low molecular weight component is observed at the end of the elution time.

  The cumulative area area (%) of the area area in the GPC elution curve is point 0 shown in FIG. 1 being 0%, which is the standard for the cumulative area area (%), toward the end of the elution time, and detection corresponding to each elution time. The view is that the intensity accumulates and an area area in the GPC elution curve is formed. A specific example of the accumulated area area is shown in FIG. In FIG. 2, a point on the baseline at a certain elution time is a point X, and a point on the GPC elution curve is a point Y. The ratio of the area surrounded by the curve AY, the line segment AX, and the line segment XY to the area area in the GPC elution curve is the value of the accumulated area area (%) at a certain elution time.

  Let Mh (wt%) be the average composition ratio of other vinyl monomer units copolymerizable with methyl methacrylate in the methacrylic resin having a weight average molecular weight component in the cumulative area of 0 to 2%. On the other hand, the average composition ratio of other vinyl monomer units that can be copolymerized with methyl methacrylate in a methacrylic resin having a cumulative area of 98 to 100%, that is, a low molecular weight is defined as Ml (wt%). FIG. 3 shows a schematic diagram of positions on the measurement graph of the accumulated area area of 0 to 2% and 98 to 100%.

  The values of Mh and Ml can be obtained by fractionating several times or several tens of times according to the column size based on the elution time obtained from GPC. The composition of the collected sample may be analyzed by a known pyrolysis gas chromatography method.

  It is preferable that the relationship of the following formula (2) is established between Mh (wt%) and Ml (wt%) in the present invention.

(Mh−0.8) ≧ Ml ≧ 0 (2)
This indicates that the high molecular weight component has an average composition of 0.8 wt% or more of other vinyl monomer units copolymerizable with methyl methacrylate than the low molecular weight component. The low molecular weight component indicates that other vinyl monomers do not necessarily have to be copolymerized. The difference between Mh (wt%) and Ml (wt%) is preferably 0.8 wt% or more for the effect of improving dissolution characteristics. More preferably, it is 1.0 wt% or more, More preferably, it is 2.0 wt% or more.

  That is, the average composition of other vinyl monomer units copolymerizable with methyl methacrylate of the methacrylic resin in the high molecular weight component is 2 wt% or more than the average composition of the low molecular weight component, so that the heat resistance and environmental test can be performed. It is preferable because the effect of improving the dissolution characteristics can be obtained while maintaining the reliability such as cracks and warpage and mechanical strength.

  As a polymerization method of the methacrylic resin which is a thickener of syrup in the present invention, two-stage suspension polymerization or emulsion polymerization is used. The two-stage polymerization is a method in which a monomer, an initiator, a chain transfer agent, and the like are further added after normal suspension polymerization or emulsion polymerization. By changing the composition of the polymer (1) and the polymer (2), a resin composition having both the characteristics of the polymer (1) and the polymer (2) can be obtained. Suspension polymerization or emulsion polymerization is advantageous for artificial marble because powdery resin beads are obtained. Other polymerization methods are not preferable because powdery resin beads cannot be obtained. As the polymerization method, suspension polymerization is preferred because suspension polymerization is shorter than emulsion polymerization. A blend of suspension polymerization or emulsion polymerization powdered resin beads is not preferable because the solubility characteristics of the high molecular weight resin beads are poor.

  It is appropriate to use a two-stage polymerization for the methacrylic resin which is the thickener of the present invention. Even with three or more stages, a methacrylic resin having the same properties as two-stage polymerization can be obtained, but this is not preferable because the polymerization time is further increased.

  The composition of the methacrylic resin that is the thickener of the present invention is such that the content of the other vinyl monomer copolymerizable with methyl methacrylate is 1 to 20 wt% of the entire methacrylic resin, and the polymer (1) The contents of each of the polymers (2) may be different. Moreover, it is not necessary to use other vinyl monomers copolymerizable with methyl methacrylate in the polymer (1).

  As for the methacrylic resin which is a thickener of this invention, it is preferable that a polymer (1) is low molecular weight and a polymer (2) is high molecular weight. More preferably, the polymerization method is a method obtained by polymerizing the polymer (1) and then polymerizing the polymer (2) in the presence of the polymer (1).

In the methacrylic resin which is the thickener of the present invention, the polymer (1) is composed of 70 to 100 wt% of methyl methacrylate monomer and at least one other vinyl monomer copolymerizable with methyl methacrylate. It is a polymer comprising 30 to 0 wt% of the monomer. More preferably, it is 20 to 0 wt% of a monomer composed of at least one other vinyl monomer copolymerizable with methyl methacrylate. More preferably, it is 15 to 0 wt% of a monomer composed of at least one other vinyl monomer copolymerizable with methyl methacrylate.
In the methacrylic resin which is the thickener of the present invention, the molecular weight of the polymer (1) is preferably 10,000 to 50,000 as the weight average weight measured by gel permeation chromatography. When the weight average molecular weight is 10,000 or less, the heat resistance is lowered, and therefore 10,000 or more is preferable. Moreover, in this case, when polymerizing the polymer (2) in the presence of the polymer (1), the molecular weight of the polymer (2) is preferable during continuous production. From the viewpoint of dissolution characteristics, 50000 or less is preferable. More preferably, it is 20000-40000, More preferably, it is 20000-30000.

In the methacrylic resin which is a thickener of the present invention, the polymer (2) is composed of 70 to 100 wt% of methyl methacrylate monomer and at least one other vinyl monomer copolymerizable with methyl methacrylate. It is a polymer composed of 0 to 30 wt% of the monomer. More preferably, it is 1-80 wt%.
In the methacrylic resin which is the thickener of the present invention, the molecular weight of the polymer (2) is preferably 110000 to 600000 as the weight average weight measured by gel permeation chromatography. From the point of mechanical strength and syrup viscosity, 110000 or more is preferable. When the molecular weight is set high, the polymerization is likely to proceed rapidly, and heat is generated to easily cause bumping of the monomer. From the point of stable production, 600000 or less is preferable. More preferably, it is 150,000 to 500,000. More preferably, it is 180000-400000.

  The methacrylic resin which is a thickener of the present invention is composed of a composition ratio Mal (wt%) of other vinyl monomer units polymerizable to methyl methacrylate of the polymer (1) and methyl methacrylate of the polymer (2). It is preferable that the relationship of the formula (3) is satisfied in the composition ratio Mah (wt%) of other vinyl monomer units that can be polymerized.

(Mah-0.8) ≧ Mal ≧ 0 (3)
The composition ratios Mal and Mah here can determine the ratios of the polymer (1) and the polymer (2) by pyrolysis gas chromatography. The composition ratios used in the preparation for obtaining each of them show almost the same value.

  The difference between Mah (wt%) and Mal (wt%) is 0.8 wt% or more from the viewpoint of dissolution characteristics. It is preferable that the polymer (2) having a high molecular weight has a larger proportion of other vinyl monomers copolymerizable with methyl methacrylate because the solubility characteristics can be improved while maintaining heat resistance and mechanical strength.

  The average particle diameter of the methacrylic resin that is the thickener of the present invention is preferably 0.05 to 0.5 mm. Since the dissolution time is shorter as the particle size is smaller, 0.5 mm or less is preferable. However, if the particle size is too small, it tends to scatter during handling, and 0.05 mm or more is preferable. More preferably, the average particle size is 0.05 to 0.4 mm. Most preferably, the average particle size is 0.1 to 0.4 mm.

  As a polymerization initiator for producing a methacrylic resin which is a thickener of the present invention, when using free radical polymerization, di-t-butyl peroxide, lauryl peroxide, dilauroyl peroxide, t-butyl peroxide are used. Peroxides such as oxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, Common azo-based radical polymerization initiators such as azobisisobutyronitrile, azobisisovaleronitrile, 1,1-azobis (1-cyclohexanecarbonitrile) can be used. You may use the above together. A combination of these radical initiators and an appropriate reducing agent may be used as a redox initiator. These initiators are generally used in the range of 0.001 to 1 wt% with respect to the monomer mixture.

  In the manufacturing method of the methacrylic resin which is the thickener of syrup of this invention, when manufacturing by radical polymerization method, in order to adjust the molecular weight of a polymer (1) and a polymer (2), it uses generally. Chain transfer agents that are used can be used. Examples of the chain transfer agent include n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, 2-ethylhexyl thioglycolate, ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate). Etc.) are preferably used. Generally, it is used in the range of 0.001 to 1 wt% with respect to the monomer mixture. The chain transfer agents used for the polymer (1) and the polymer (2) may be the same or different. The amount of chain transfer agent of polymer (1) and polymer (2) is determined depending on the desired molecular weight.

  The methacrylic resin, which is the thickener of the present invention, has a shorter production time without impairing the mechanical strength and durability of conventional artificial marble. While improving the productivity of syrup, it is possible to reduce the production cost by reducing the amount of methacrylic resin used, which is suitable for artificial marble applications.

  The methacrylic resin, which is the thickener of the present invention, can be used for thickeners such as paints and adhesives as well as for artificial marble syrup.

This will be described more specifically with reference to the following examples and comparative examples.
<Raw material>
The raw materials used are as follows. Methyl methacrylate: manufactured by Asahi Kasei Chemicals (2.5 ppm of 2,4-di-6-tert-butylphenol) is added as a polymerization inhibitor )
Methyl acrylate: manufactured by Mitsubishi Chemical (added with 14 ppm of 4-methoxyphenol manufactured by Kawaguchi Chemical Industry as a polymerization inhibitor)
n-octylmercaptan (N-octylmercaptan): Arkema Lauroyl peroxide: Nippon Oil & Fats Tricalcium phosphate: Nippon Kagaku Kogyo Co., Ltd., used as a suspending agent Calcium carbonate: Shiraishi Made as a suspension agent Sodium lauryl sulfate: Wako Pure Chemical Industries, used as a suspension aid

[I. Polymerization of resin]
1. Polymerization of resin The method for producing the resin is shown below. The blending amounts are shown in Table 1, and the charged composition of the monomer and the ratio of the polymers, and the measurement results of the weight average molecular weight of each polymer are shown in Table 2.
(Resin 1)
Into a 10 L glass reactor, the raw materials for the polymer (1) were added in the amounts shown in Table 1, stirred and mixed, and the polymerization reaction was substantially terminated by suspension polymerization at a reaction temperature of 80 ° C. for 150 minutes. Thus, a polymer (1) was obtained. This polymer (1) was sampled and the polymerization average molecular weight was measured by GPC. Thereafter, the polymerization system containing the polymer (1) was maintained at 80 ° C. for 60 minutes, and then the raw material of the polymer (2) was charged into the compounding amount reactor shown in Table 1, and subsequently at 80 ° C. for 120 minutes. The suspension was subjected to suspension polymerization, subsequently heated to 92 ° C. at a rate of 1 ° C./min, and then aged for 60 minutes to substantially complete the polymerization reaction. Next, in order to cool to 50 ° C. and dissolve the suspending agent, 20 wt% sulfuric acid was added, washed and dehydrated and dried to obtain methacrylic resin beads. The polymerization average molecular weight of the methacrylic resin beads is measured by GPC, and based on the GPC elution curve of the polymer (1), the ratio of the polymer (1) is multiplied to obtain the GPC elution curve of the methacrylic resin beads. The GPC portion of the polymer (1) was removed, and the weight average molecular weight of the polymer (2) was determined.

(Resin 2, 3, 9, 15, 16, 22)
Polymerization was carried out in the same manner as Resin 1 with the formulation shown in Table 1, to obtain methacrylic resin beads.
(Resin 4)
Into a 60 L reactor, the raw materials of the polymer (1) were charged with the blending amounts shown in Table 1 and mixed with stirring. Suspension polymerization was carried out at a reactor reaction temperature of 80 ° C. for 150 minutes. Combined (1) was obtained. This polymer (1) was sampled and the polymerization average molecular weight was measured by GPC.
Thereafter, the polymerization system containing the polymer (1) was maintained at 80 ° C. for 60 minutes, and then the raw material of the polymer (2) was charged into the blending amount reactor shown in Table 1, and subsequently at 90 ° C. The suspension was subjected to suspension polymerization, subsequently heated to 92 ° C. at a rate of 1 ° C./min, and then aged for 60 minutes to substantially complete the polymerization reaction. Next, in order to cool to 50 ° C. and dissolve the suspending agent, 20 wt% sulfuric acid was added, washed and dehydrated and dried to obtain methacrylic resin beads. The polymerization average molecular weight of the methacrylic resin beads is measured by GPC, and based on the GPC elution curve of the polymer (1), the ratio of the polymer (1) is multiplied to obtain the GPC elution curve of the methacrylic resin beads. The GPC portion of the polymer (1) was removed, and the weight average molecular weight of the polymer (2) was determined.
(Resin 5-8, 13, 14, 17, 18, 20, 21, 23, 24)
Polymerization was carried out in the same manner as Resin 4 with the formulation shown in Table 1, to obtain methacrylic resin beads.
(Resin 10)
The raw material of the polymer (1) was put into a 60 L reactor and the mixing amount shown in Table 1 was added and stirred and mixed. Suspension polymerization was carried out at 80 ° C. for 150 minutes, followed by 92 ° C. at 1 ° C. / After raising the temperature at a rate of min, the mixture was aged for 60 minutes to substantially complete the polymerization reaction. Next, in order to cool to 50 ° C. and dissolve the suspending agent, 20 wt% sulfuric acid was added, washed and dehydrated and dried to obtain methacrylic resin beads. The methacrylic resin beads were sampled and the polymerization average molecular weight was measured by GPC.
(Resin 11, 12)
Polymerization was carried out in the same manner as Resin 10 with the formulation shown in Table 1, to obtain methacrylic resin beads.

[II. Measurement of resin molecular weight and composition]
2. Measuring and measuring apparatus for weight average molecular weight of methacrylic resin: Gel Permeation Chromatography (LC-908) manufactured by Nippon Analytical Industry
Column: 1 JAIGEL-4H and 2 JAIGEL-2H in series connection In this column, the high molecular weight elutes early, and the low molecular weight elutes slowly.
Detector: RI (differential refraction) detector Detection sensitivity: 2.4μV / sec
Sample: 0.450 g of methacrylic resin in chloroform 15 ml Injection amount: 3 ml
Developing solvent: chloroform, flow rate 3.3 ml / min
Under the above conditions, the RI detection intensity with respect to the elution time of the methacrylic resin was measured. The average molecular weight of the methacrylic resin was determined based on the area area in the GPC elution curve and the calibration curve.

The following 10 methacrylic resins (manufactured by EasiCal PM-1 Polymer Laboratories) having different molecular weights and known monodispersed weight average molecular weights were used as standard samples for calibration curves. Weight average molecular weight
Standard sample 1 1,900,000
Standard sample 2 790,000
Standard sample 3 281,700
Standard sample 4 144,000
Standard sample 5 59,800
Standard sample 6 28,900
Standard sample 7 13,300
Standard sample 8 5,720
Standard sample 9 1,936
Standard sample 10 1,020
When the polymer (1) and the polymer (2) are mixed, the GPC elution curve of the polymer (1) alone is measured in advance to determine the weight average molecular weight, and the polymer (1) is present. The GPC elution curve in which the polymer (1) and the polymer (2) are mixed by multiplying the GPC elution curve of the polymer (1) by the ratio (the charge ratio was used in the present application) and the detection intensity at the elution time. By subtracting from GPC, a GPC elution curve of the polymer (2) alone is obtained. From this, the weight average molecular weight of the polymer (2) was determined.

  Further, the peak weight average molecular weight (Mp) in the GPC elution curve is determined from the GPC elution curve and the calibration curve. The content of a weight average molecular weight component of 1/5 or less of Mp is determined as follows.

  First, the area area in the GPC elution curve of methacrylic resin is obtained. The area area in the GPC elution curve indicates the hatched portion shown in FIG. The specific method is as follows. First, the GPC elution curve obtained from the GPC elution curve obtained from the GPC measurement and the detection intensity by RI (differential refraction detector) is crossed with the GPC elution curve by subtracting the automatically drawn baseline obtained by the measuring instrument. Define A and point B. Point A is a point where the GPC elution curve at the beginning of the elution time and the baseline intersect. Point B is a position where, as a general rule, the weight average molecular weight is 500 or more and the base line and the elution curve intersect. If they do not intersect, point B is the RI detection intensity value of the elution time when the weight average molecular weight is 500. The hatched portion surrounded by the GPC elution curve and the base line between points A and B is the area in the GPC elution curve. This area is the area of the GPC elution curve. In the present application, since a column eluted from a high molecular weight component is used, a high molecular weight component is observed at the beginning of the elution time (point A side), and a low molecular weight component is observed at the end of the elution time (point B side).

The area area in the GPC elution curve is divided by the elution time corresponding to the weight average molecular weight of 1/5 of Mp, and the area area in the GPC elution curve corresponding to the weight average molecular weight component of 1/5 or less of Mp is obtained. From the ratio of the area and the area of the GPC elution curve, the ratio of the weight average molecular weight of 1/5 or less of Mp was determined.
3. Composition analysis of methacrylic resin The composition analysis of methacrylic resin was performed by pyrolysis gas chromatography and mass spectrometry.

Pyrolysis device: PY-2020D made by FRONTIER LAB
Column: DB-1 (length 30 m, inner diameter 0.25 mm, liquid phase thickness 0.25 μm)
Column temperature program: held at 40 ° C. for 5 minutes, then heated to 320 ° C. at a rate of 50 ° C./min, then held at 320 ° C. for 4.4 minutes Pyrolysis furnace temperature: 550 °
Column inlet temperature: 320 ° C
Gas chromatography: Agilent GC6890
Carrier: pure nitrogen, flow rate 1.0 ml / min
Injection method: Split method (split ratio 1/200)
Detector: JEOL mass spectrometer Automass Sun
Detection method: Electron impact ionization method (ion source temperature: 240 ° C., interface temperature: 320 ° C.)
Sample: 10 μl of 10 g chloroform solution of 0.1 g methacrylic resin

A sample was collected in a platinum sample cup for a thermal decomposition apparatus, vacuum-dried at 150 ° C. for 2 hours, and then the sample cup was placed in a thermal decomposition furnace, and composition analysis of the sample was performed under the above conditions. The composition ratio of the methacrylic resin was determined based on the peak area on total ion chromatography (TIC) of methyl methacrylate and methyl acrylate and the calibration curve of the following standard sample.
Preparation of standard sample for calibration curve: The ratio of methyl methacrylate and methyl acrylate is (methyl methacrylate / methyl acrylate) = (100% / 0%), (98% / 2%), (94% / 6% ), (90% / 10%) (80% / 20%) were added to 50 g of each of the five solutions in total, 0.25% lauroyl peroxide and 0.25% n-octyl mercaptan. Each of these mixed solutions was put into a 100 cc glass ampule bottle, and the air was replaced with nitrogen and sealed. The glass ampoule bottle was placed in an 80 ° C. water bath for 3 hours and then in an oven at 150 ° C. for 2 hours. After cooling to room temperature, the glass was crushed and the methacrylic resin inside was taken out and subjected to composition analysis. A graph of (methyl acrylate area value) / (methyl methacrylate area value + methyl acrylate area value) and methyl acrylate charge ratio obtained by measurement of a standard sample for a calibration curve is used as a calibration curve. It was.

4). Measurement of composition ratio of vinyl monomer copolymerizable with methyl methacrylate in high molecular weight component and low molecular weight component of methacrylic resin In this measurement, the molecular weight component has a cumulative area of 0-2% and 98-100% Perform composition analysis of molecular weight components. The cumulative area area (%) of the area area in the GPC elution curve is point 0 shown in FIG. 1 being 0%, which is the standard for the cumulative area area (%), toward the end of the elution time, and detection corresponding to each elution time. The view is that the intensity accumulates and an area area in the GPC elution curve is formed. A specific example of the accumulated area area is shown in FIG. In FIG. 2, a point on the baseline at a certain elution time is a point X, and a point on the GPC elution curve is a point Y. The ratio of the area enclosed by the curve AX, the line segment AB, and the line segment XY to the area area in the GPC elution curve is the value of the accumulated area area (%) at a certain elution time. A molecular weight component having a cumulative area of 0 to 2% and a molecular weight component being 98 to 100% were separated from the column based on the corresponding elution time, and the composition analysis was performed. Measurement and fractionation of each component are as follows. The same apparatus and conditions were used.
Perform two fractions and 10 μl of the fractioned sample is 3. The sample was collected in a platinum sample cup for a pyrolysis apparatus of the pyrolysis gas chromatography analysis and mass spectrometry method used in the above, and dried in a vacuum dryer at 100 ° C. for 40 minutes. 3. The composition of the methacrylic resin corresponding to the accumulated area area fractionated under the same conditions as above was determined.

[III. Measurement of characteristics of resin beads]
5. Particle size measurement The particle size distribution of the resin beads was measured and classified using a sieve. The size of the mesh of the sieve is 0.5mm, 0.425mm, 0.355mm, 0.3mm, 0.25mm, 0.15mm from the top, and put a saucer at the bottom and vibrate with a shaker. separated.
6). Dissolution test Place water in a water bath with a stirrer and heat to 45 ° C. A 110 cc screw bottle (diameter 50 mm) is charged with 16 g of methacrylic resin, 64 g of methyl methacrylate monomer (in the case of 20 wt% methacrylic resin) and a rotor, and the lid of the screw bottle is closed. Put the screw bottle in the water bath and start the measurement after rotating the stirrer. The time until the methacrylic resin composition in the bottle is dissolved in methyl methacrylate is measured.
7). Viscosity measurement of syrup A B-type viscometer is used as a measuring instrument and SB2 is used as a rotor. 6). The syrup prepared by the method is cooled to room temperature (23 ± 3 ° C.) with stirring. Weigh syrup solution into a 40 cc measuring tube. Viscosity measurement is started by installing a measuring tube on the viscometer. Viscosity is measured at a rotor speed of 60 rpm. (When the measurement range is exceeded at 60 rpm, the rotational speed is decreased.) The viscosity at the rotational speed of the rotor of 6 rpm is also measured, and the numerical value of the viscosity is compared to determine the accuracy.
8). The methacrylic resin beads obtained by pelletizing polymerization were extruded at a resin temperature of 240 ° C. to 250 ° C. using a twin screw extruder to obtain pellets.
9. Measurement of VICAT softening temperature Molding machine: 30t press molding machine Test piece: 4mm thickness
Measurement conditions: conforming to ISO 306 B50 The VICAT softening temperature was determined under the above conditions.

[Examples 1 to 13, Comparative Examples 1 to 9]
Conventionally, the resin 14 of Comparative Example 1 is often used as a syrup thickener. The composition of syrup is 80 wt% methyl methacrylate monomer and 20 wt% resin 14, and the viscosity of syrup is about 400 mPa · s. We have developed a syrup that reduces manufacturing costs while maintaining the mechanical strength and durability of conventional artificial marble.
(Heat-resistant)
The heat resistance of the methacrylic resin tends to increase as the amount of other vinyl monomers copolymerizable with methyl methacrylate decreases. (VICAT softening temperature comparison: Comparative Example 1 is 105 ° C., Comparative Example 2 is 110 ° C.) The heat resistance of the methacrylic resin that is a thickener may affect the artificial marble product. Therefore, it is considered that higher heat resistance is preferable.
Moreover, it is considered from Comparative Examples 1 and 2 that the higher the heat resistance, the longer the dissolution time. From Comparative Example 2 and Example 7, it is considered that the thickener of the present invention has improved solubility even with the same degree of heat resistance.
(Particle size measurement)
Table 4 shows the particle size distribution by the sieve. The 10 L beaker product has a smaller overall particle size.
(Resin concentration and solution viscosity)
Table 5 shows the results of resin concentration and solution viscosity. In conventional syrup, 20 wt% of the resin 14 of Comparative Example 1 is often added to 80 wt% of methyl methacrylate and dissolved while stirring at an average of 45 ° C. The viscosity is about 400 mPa · s at a temperature of about 23 ° C. Some of the other resins were dissolved at a concentration of 20 wt%, but it was found that the viscosity varies depending on the resin. Compared with the molecular weight, the higher the molecular weight, the higher the viscosity of the syrup. Therefore, the concentration of the resin was set based on the molecular weight.

Molecular weight around 90000: Resin concentration 26wt%
Molecular weight around 110000: Resin concentration 24wt%
Molecular weight around 145000: Resin concentration 22wt%
Molecular weight around 195000: Resin concentration 20wt%
Molecular weight around 235,000: Resin concentration 18.5 wt%
Molecular weight around 260000: Resin concentration 18wt%
Molecular weight around 400,000: Resin concentration 15wt%
(Effect of polymerization method)
Comparative Examples 1 to 3 are resins prepared by a single polymerization that has been conventionally performed. Examples 1 to 10 are resins prepared by performing suspension polymerization twice. Comparing the amount of methyl acrylate with a resin having a similar molecular weight, the dissolution time of the examples is shorter. Therefore, it is considered that the twice-polymerized product has better solubility characteristics than the once-polymerized product.
(Dissolution time comparison)
Table 4 shows the dissolution time for each particle size when the syrup viscosity is kept constant. The smaller the particle size, the shorter the dissolution time. One of the objects of the present invention is to shorten the dissolution time. I want to shorten the melting time of the conventional product. Therefore, it was decided to shorten the melting time target value by 10 minutes or more from the melting time of the conventional product. Examples 1-10 all achieve the desired dissolution characteristics. Therefore, the dissolution characteristics were evaluated by comparing the examples and comparative examples.
(Amount of other vinyl monomers copolymerizable with methyl methacrylate and dissolution time)
In Table 4, the dissolution time of Comparative Example 4 with 0.5 wt% methyl acrylate is longer than the dissolution time of Comparative Example 1. The dissolution time of Example 7 with 1.2 wt% methyl acrylate is shorter than the dissolution time of Comparative Example 1 by 10 minutes or more. Therefore, it is considered that the target dissolution time is reached when the amount of methyl acrylate is about 1 wt% or more.
(Molecular weight and dissolution time)
In Table 4, Comparative Example 6 having a high molecular weight does not achieve the desired dissolution characteristics. In Comparative Example 5, the molecular weight is small, and the strength of the artificial marble can be reduced. Examples 3 and 9 both achieve the desired dissolution characteristics. The set value of the molecular weight for achieving the desired dissolution property is considered to be about 110000-400000.
(Mw / Mn comparison)
Mw / Mn increases as the difference in molecular weight between the polymer (1) and the polymer (2) increases. This is considered to indicate that the molecular weight distribution is widened. The solubility of Example 4 with Mw / Mn of 2.5 achieves the goal. Example 12 with Mw / Mn of 2.2 does not achieve the objective. Therefore, Mw / Mn is preferably 2.3 or more.
(Mp comparison)
The greater the difference in molecular weight between the polymer (1) and the polymer (2), the wider the molecular weight distribution, and the weight average molecular weight component amount that is 1/5 or less of the peak weight average molecular weight (Mp) obtained from the GPC elution curve. Is expected to increase. The weight average molecular weight component amount of 1/5 or less of the peak weight average molecular weight (Mp) obtained from the GPC elution curve of Comparative Example 7 is 7.6, and the solubility of Comparative Example 7 does not achieve the purpose. The weight average molecular weight component amount of 1/5 or less of the peak weight average molecular weight (Mp) obtained from the GPC elution curve of Example 5 is 1.8, and the target solubility is achieved.
In addition, when the weight average molecular weight component amount of 1/5 or less of the peak weight average molecular weight (Mp) obtained from the GPC elution curve is increased from 30%, the ratio of the low molecular weight is increased as in Comparative Example 8, and the mechanical strength is increased. There is concern about the decline.
As mentioned above, 8-30% of the weight average molecular weight component amount of 1/5 or less of the peak weight average molecular weight (Mp) obtained from a GPC elution curve is preferable.
(Comparison of Mh and Ml)
Average composition ratio Mh of other vinyl monomer units copolymerizable with methyl methacrylate in methacrylic resin having a weight average molecular weight component having a cumulative area (%) in the GPC elution curve of methacrylic resin of 0 to 2%. (Wt%) and the average composition ratio Ml (wt) of other vinyl monomer units copolymerizable with methyl methacrylate in a methacrylic resin having a weight average molecular weight component having a cumulative area area (%) of 98 to 100% %).
In Table 3, when comparing Example 11 having almost the same amounts of Mh and Ml and Example 10 having more Mh, the solubility of Example 10 is higher.
In Example 7, Mh-Ml is 0.9%, and it is considered that the difference between Mh and Ml is preferably 0.8 or more.

(Mah and Mal)
The composition ratio of the other vinyl monomer copolymerizable with the methyl methacrylate of the polymer (1) is Mal (wt%), and the other vinyl monomer copolymerizable with the methyl methacrylate of the polymer (2). The composition ratio of the unit is Mah (wt%).
As in the case of Mh and Ml, the higher the amount of high molecular weight Mah, the higher the solubility. From Examples 7, 10, and 11, it is considered that the difference between Mah and Mal is preferably 0.8 or more. (Molecular weight of polymer (1))
In Example 12 in which the molecular weight of the polymer (1) was set to 7000, the VICAT softening temperature was 102 ° C., and the temperature was lower than 105 ° C. in Example 3 where the amount of methyl acrylate was the same. There is concern that the physical properties of the artificial marble may be lowered when the molecular weight is low. In Comparative Example 9 set to 60000, the dissolution characteristics do not reach the purpose. Therefore, it is considered that the molecular weight range of the polymer (1) is preferably 10,000 to 50,000.
(Molecular weight of polymer (2))
In Comparative Example 5 in which the molecular weight of the polymer (2) is set to 100,000, the total molecular weight is 81,000 and the amount of resin used is increased by about 30%. In Comparative Example 6 set to 700,000, the dissolution characteristics do not reach the purpose. It is considered that the molecular weight range of the polymer (2) is preferably 110000 to 60000.
(Ratio of polymer (1) to polymer (2))
In Table 4, Comparative Example 7 in which the ratio of the polymer (1) is set to 5 wt% and Comparative Example 8 in which the ratio of polymer (1) is set to 35 wt% do not reach the intended dissolution characteristics. Example 5 in which the ratio of the polymer (1) was set to 10 wt% and Example 6 in which the ratio was set to 27% both achieved the desired dissolution characteristics. Therefore, it is considered that the ratio of the polymer (1) is preferably 7 to 30 wt%.
(When the molecular weight of the polymer (1) is high)
Example 13 is a case where the molecular weight of the polymer (1) is set high. The effect of double polymerization is not obtained with the same dissolution characteristics as those of Comparative Example 3 which is a single polymerization product. Therefore, it is considered preferable to set the molecular weight of the polymer (1) low.
(Particle size of resin)
In the table, all resins have an average particle size in the range of 0.05 to 0.5 mm.

  The thickener of the present invention realizes shortening of syrup production time without impairing the mechanical strength and durability of conventional artificial marble. While improving the productivity of syrup, it is possible to reduce the production cost by reducing the amount of methacrylic resin used, which is suitable for syrup thickener applications.

It is explanatory drawing regarding the GPC area of the methacryl resin in this invention. The vertical axis of the graph shows RI detection intensity (mV), the lower part of the horizontal axis of the graph shows elution time (min.), And the upper part shows the cumulative area area (%) relative to the entire GPC area area. It is the figure which showed an example of the accumulation area area. It is the schematic which shows the position of 0-2% of accumulation area areas, and 98-100% of accumulation area areas on a GPC elution curve measurement graph.

Explanation of symbols

1. Elution curve Base line

Claims (6)

A methacrylic resin comprising 99 to 80 wt% of methyl methacrylate monomer units and 1 to 20 wt% of other vinyl monomer units copolymerizable with at least one methyl methacrylate, the gel permeation of the methacrylic resin The weight average molecular weight measured by chromatography (GPC) is 100,000 to 400,000, and the methacrylic resin component is 1/5 or less of the peak weight average molecular weight (Mp) obtained from the GPC elution curve. A thickener comprising 8 to 30% methacrylic resin. The methacrylic resin has an average particle diameter of 0.05 to 0.5 mm, and the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) are in the relationship of the formula (1). 2. The thickener according to claim 1, comprising a methacrylic resin.
Mw / Mn ≧ 2.3 (1) Average composition ratio of other vinyl monomer units copolymerizable with methyl methacrylate in the methacrylic resin in the methacrylic resin having a weight-average molecular weight component having a cumulative area (%) in the GPC elution curve of the methacrylic resin of 0 to 2%. Average composition ratio Ml of other vinyl monomer units copolymerizable with methyl methacrylate in a methacrylic resin having a weight average molecular weight component with Mh (wt%) and a cumulative area area (%) of 98 to 100% The thickener according to claim 1 or 2, wherein the thickener is a methacrylic resin having the relationship of the formula (2).
(Mh−0.8) ≧ Ml ≧ 0 (2) It is a manufacturing method of the thickener which consists of a methacryl resin of Claim 1, Comprising: First, 70-100 wt% of methyl methacrylate monomers and 30-0 wt% of other vinyl monomers copolymerizable to methyl methacrylate are added. After polymerizing and polymerizing the polymer (1) having a weight average weight of 10,000 to 50,000 measured by gel permeation chromatography so as to be 7 to 30 wt% based on the entire methacrylic resin, The polymerization is continued in the presence of the polymer (1), and the polymer (2) having a weight average molecular weight of 110,000 to 600,000 is polymerized to 93 to 70 wt% with respect to the entire methacrylic resin. A method for producing a thickener comprising a methacrylic resin. 5. The method for producing a thickener according to claim 4, wherein the methacrylic resin comprises a methacrylic resin having a weight average molecular weight of 100,000 to 400,000 and an average particle diameter of 0.05 to 0.5 mm. . Composition ratio Mal (wt%) of other vinyl monomer copolymerizable with methyl methacrylate of polymer (1) and other vinyl monomer copolymerizable with methyl methacrylate of polymer (2) The method for producing a thickener according to claim 4 or 5, wherein the unit composition ratio Mah (wt%) is made of a methacrylic resin having a relationship of the formula (3).
(Mah-0.8) ≧ Mal ≧ 0 (3)

Images