KR20190019727A - Acrylate-based transparent laminated molded article and method for manufacturing the same - Google Patents

Abstract

The present invention relates to an acrylate-based laminated molded article which is suitable for being used in fields of requiring high mechanical properties such as an aquarium and interior by having sufficient strength as well as good productivity, quality stability and post processability; and a method for manufacturing the same. The method for manufacturing an acryl-based transparent laminated molded article of the present invention comprises the steps of: partially polymerizing an acrylate-based monomer to prepare an acryl-based syrup; preparing an acryl-based complex syrup by including an initiator in the acryl-based syrup; and manufacturing an acryl-based laminated molded article by injecting the complex syrup between acryl-based sheets and casting the same so that an adhesive layer is formed. According to the present invention, the acryl-based transparent laminated molded article does not generate an aggregate during the manufacturing process, and a laminated molded article integrated by overlapping and bonding acrylate-based sheets has stable quality that is free from bubbles or gel points in the molded article and is excellent in transparency, impact resistance, solvent resistance, coloring resistance, processability and strength. The present invention can provide an acrylate-based laminated molded article which has excellent transparency, impact resistance, solvent resistance, coloring resistance, processability and strength, and is useful in an industrial field such as an optical material and adhesive, particularly a field of the optical material, and can provide an extra-large stereoscopic acryl transparent molded article having stable quality, and a method for manufacturing the same.

Description

[0001] The present invention relates to a transparent laminated molded article and a method for producing the same,

The present invention relates to an acrylic laminated body suitable for use in fields where productivity, quality stability and post-processability are good and sufficient strength is required and high mechanical properties such as an aquarium and interior are required, and a method for producing the same.

Acrylate molded articles are excellent in transparency and weatherability and are also excellent in mechanical properties such as tensile strength and elastic modulus, surface gloss, chemical resistance, light weight, safety, processability and adhesiveness, , Household appliances, office automation equipment, signboards, various building materials, adhesives, reforming agents for plastic materials, and the demand is also increasing.

Particularly in recent years, because of its excellent transparency, it has been used as a high-performance optical material such as a plate-like sheet, a light guide plate, and a film for a liquid crystal display. In the case of producing a sheet, Due to poor fluidity and high molecular weight, bubbles, deformation, and distortion are caused, resulting in problems in commercialization.

Particularly, sheet-like sheets are lighter than glass and have excellent impact resistance. However, in order to increase the thickness of the product, an acrylate resin having high mechanical strength and high fluidity is required. However, , It is difficult to produce a thick large sheet due to an increase in defective points such as bubbles in the inside or unevenness of optical characteristics due to the formation of gel.

In order to solve the problems of the prior art as described above, the present invention provides a method of producing a laminated acrylic molded article which does not generate bubbles or gels due to polymerization of monomers when producing thick acrylic molded articles.

The present invention also provides a method for producing an acrylic laminated molded article in which transparency is further increased by preventing interfacial formation of an adhesive surface caused by a conventional solvent adhering method or the like even though a laminated body of acrylic sheets is manufactured.

The present invention also relates to a method for producing a new acrylic laminated molded article in which transparency and mechanical properties are further improved by preventing the formation of a gel due to bubbles or heat shots on an acrylic sheet constituting the laminated molded article and on the adhesion surface between the sheet and the sheet .

In addition, the present invention can effectively prevent the reaction from proceeding unnecessarily by maintaining a uniform exothermic reaction and keeping the end point of the polymerization reaction constant without containing any foreign substance such as a polymerization inhibitor, thereby facilitating the control of viscosity, conversion and molecular weight, And a transparent acrylic laminated molded article produced from the transparent laminated molded article is provided.

The present invention also solves the risk factors due to the exothermic reaction by the casting process in the production of sheets and molded articles. That is, as a super large acrylate-based laminated molded body, it is required to have excellent transparency, impact resistance, solvent resistance, coloring resistance, workability and rigidity, and also a new manufacturing method for relieving heat due to a stable product without bending, to provide.

Further, the present invention is characterized in that the acrylate-based molded article of the present invention has an adhesive layer between the acrylate-based sheets, and the acrylate-based resin dissolves the surface of the acrylate-based sheet during the bulk polymerization, And it is possible to provide a property that a high impact resistance is obtained as the thickness of the layer increases.

Further, in the present invention, since the refractive index of the adhesive layer is the same as that of the acrylate sheet, or if the difference is 0.005 or less depending on the molecular weight and the degree of polymerization, there is no influence on the transparency and each layer is formed even if the refractive index according to temperature changes, The transparency change provides an acrylic laminated molded article.

The above and other objects of the present invention can be achieved by the present invention described below.

According to an aspect of the present invention, there is provided a method for producing an acrylic syrup, comprising the steps of: partially mixing an acrylate monomer to prepare an acrylic syrup;

An acrylic-based complex syrup preparation step comprising an initiator in an acrylic syrup, and

Adding the complex syrup between acrylic sheets and casting to form an adhesive layer to produce an acrylic laminated molded article,

Based on the weight of the acrylic-based transparent laminated molded article.

In one embodiment of the present invention, the acrylic sheet may be prepared by casting the acrylic complex syrup.

In one embodiment of the present invention, the acrylic syrup may contain 0.005 to 1 part by weight of a radical initiator having a half-life temperature of 10 hours to 50 to 80 ° C, based on 100 parts by weight of the acrylic monomer.

In one embodiment of the present invention, the acrylic syrup may have a polymerization conversion rate of 5 to 50% by weight of the acrylic monomer.

In an embodiment of the present invention, the acrylic syrup has a viscosity of 2,000 to 4,000 cps, a weight average molecular weight (Mw) and a number average molecular weight of 600,000 to 800,000 and 150,000 to 350,000, respectively, and a relationship between a weight average molecular weight and a number average molecular weight Mw / Mn = 2.0 to 3.5.

In one aspect of the present invention, the acrylic syrup may be one produced by bulk polymerization.

In one aspect of the present invention, the formation of the sheet and the bonding layer joining the sheet and the sheet may be formed by casting.

In an embodiment of the present invention, the difference in refractive index between the sheet and the adhesive layer in the transparent laminated formed article may be 0.005 or less.

In one aspect of the present invention, the complex syrup may further comprise at least one selected from a crosslinking agent, a polymerization inhibitor, a polymerization regulator, an ultraviolet ray inhibitor, and a heat stabilizer.

Another aspect of the present invention is a method for producing an acrylic syrup, comprising the steps of: preparing an acrylic syrup by partial bulk mixing so that the acrylate monomer has a conversion of 10 to 30%

An acrylic-based complex syrup preparation step comprising an initiator in an acrylic syrup, and

Preparing an acrylic laminated molded article including a laminated structure of an acrylic sheet, an adhesive layer, and an acrylic sheet by injecting the complex syrup between the acrylic sheets and casting the same to form an adhesive layer;

Based on the weight of the acrylic-based transparent laminated molded article.

The acrylate resin of the present invention is excellent in fluidity and is suitable for casting molding, coating and adhesive, and a molded article obtained from this resin is useful as an optical material or a structural material because of its high tensile properties, solvent resistance, heat resistance and impact resistance.

The acrylic transparent laminated molded article of the present invention is free from agglomerates during the manufacturing process, and the laminated molded article in which the acrylate type sheets are superposed and joined together has transparency, impact resistance, solvent resistance, resistance to coloring, And it has stable quality with excellent strength.

The present invention can provide an acrylate-based laminated molded article excellent in transparency, impact resistance, solvent resistance, color proofness, workability, and strength useful in the industrial field such as optical materials and adhesives, particularly in the field of optical materials, A three-dimensional acrylic transparent molded article and a method for producing the same.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described more fully hereinafter with reference to the accompanying drawings, It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention is merely intended to effectively describe a specific embodiment and is not intended to limit the invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The present invention relates to an acrylic resin composition which is obtained by injecting and sintering a complex syrup containing an initiator into an acrylate syrup containing an acrylate-based polymer and an acrylic monomer between acrylate-based sheets made of an acrylate-based resin, The present invention relates to a three-dimensional acrylate transparent laminated molded article and a method for producing the same.

That is, the present invention relates to an acrylate-based transparent laminated molded article having excellent transparency and mechanical properties by injecting an acrylate-based complex syrup between an acrylate-based sheet and a sheet and casting the same.

Further, the acrylate-based sheet of the present invention can be produced by preparing an acrylate-based syrup, adding an additive such as an initiator or a cross-linking agent if necessary, and then casting it in a mold, The present invention provides an acrylate transparent laminated molded article which can be used in various applications such as optics and which can exclude the formation of a gel, and a method for producing the same.

Hereinafter, the configurations of the present invention will be described in detail.

The acrylate syrup and sheet of the present invention can be homogeneously molded by controlling the uniformity of the polymerization temperature and time with the low temperature initiator and the exothermic control. The production of the acrylate-based laminated molded article by the acrylate- It is preferable to control the process conditions such as sheet production in order to uniformly mold the acrylate-based syrup by injecting a component containing an initiator and performing bulk polymerization (casting and bonding).

In one embodiment of the present invention, the acrylic monomer is not particularly limited as long as it can produce an acrylic sheet. Acrylic acid or methacrylic acid having acrylic acid or methacrylic acid or CH2 = CR) COOR ₂ , R is H, methyl or n-butyl, especially methyl and n-butyl, (E. G., Optionally halo or hydroxy-substituted hydrocarbyl), especially C1-8-alkyl, C6-10-cycloalkyl or C6-10-aryl groups. Specific examples of such monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, isobornyl Vinyl esters of acrylic acid and methacrylic acid such as methacrylate, benzyl methacrylate, phenyl methacrylate and isobornyl acrylate, and acrylic acid and methacrylic acid such as hydroxyethyl methacrylate and hydroxypropyl methacrylate ≪ / RTI >

Specific examples of the acrylate resin of the present invention include a homopolymer having alkyl methacrylate as a main component or an alkyl methacrylate monomer having an alkyl group having 1 to 12 carbon atoms, such as methyl methacrylate, ethyl methacrylate, decyl methacrylate And alkyl methacrylate selected from the group consisting of 2-ethylhexyl methacrylate, and 2-ethylbutyl methacrylate.

In the present invention, the acrylic polymer produced by using the acrylic monomer means one or two or more polymers selected from the acrylic monomers, and also includes various radical copolymers containing 50% by weight or more of an acrylic monomer. Since it is commonly known in the art, a further explanation will be omitted.

Specifically, as one example of producing the acrylic syrup according to the present invention, more specific examples include 100 parts by weight of a monomer containing 50% by weight or more of an acrylic monomer, 90% by weight or more of an alkyl methacrylate monomer 100 parts by weight of a monomer containing 10 wt% or less of a monomer containing at least one of acrylic acid and methacrylic acid and 0.005 to 1 part by weight of an organic peroxide or azo compound having a half-life temperature of 50 to 80 DEG C for 10 hours And a middle molecular weight acrylate resin.

In the present invention, the acrylic syrup is a syrup having a conversion of the polymer composition of 5 to 50% by weight, preferably 10 to 30% by weight, more preferably 10 to 15% by weight. The acrylic syrup preferably has a viscosity of 2,000 To 4,000 cps, and the weight average molecular weight (Mw) and number average molecular weight are 600,000 to 800,000 and 150,000 to 350,000, respectively, and the relationship between the weight average molecular weight and the number average molecular weight satisfies Mw / Mn = 2.0 to 3.5. The reason for this is that the above-mentioned syrup is a middle molecular weight acrylate resin having more excellent fluidity and viscoelasticity, and an acrylate-based resin having excellent tensile properties, impact resistance, processing stability, reproducibility and excellent adhesiveness at high- The sheet and the laminated molded article can be produced. However, the present invention is not limited thereto as long as it adopts the manufacturing method of the present invention.

The present invention relates to a process for producing a high molecular weight acrylate-based sheet by using an acrylate-based syrup as a preliminary polymer, adding an initiator and, if necessary, a cross-linking agent, An acrylate-based transparent laminated molded article excellent in impact resistance, which is obtained by injecting and bonding an acryl-based complex syrup containing the acrylate-based syrup as a raw material, is provided.

The acrylic syrup according to the present invention is prepared by adding various additives including an initiator and a cross-linking agent, if necessary, to prepare a complex syrup and casting it into a mold. That is, for example, by using a cell casting method in which the above-described complex syrup is provided with a spacer between two glass plate (or metal plate) molds, the above-mentioned acrylate complex syrup is poured, . In order to produce a sheet having better smoothness, it is preferable to perform bulk polymerization using a material having a high elasticity such as a glass plate or a metal plate rather than the elasticity of the sheet, but the present invention is not limited thereto.

Next, a method for producing the acrylic transparent laminated molded article of the present invention will be explained.

The acrylate-based transparent laminated molded article of the present invention can be produced by the above-described acrylic sheet or between two surfaces of a transparent acrylate sheet which is an extruded sheet or a casting sheet which is not conventionally produced by syrup, To form a three-dimensional structure constituting an adhesive layer by bulk polymerization of the acrylate composite syrup of the present invention.

The acrylate-based complex syrup components constituting the adhesive layer of the present invention are dissolved or anchored on the surface of the sheet during the polymerization process to increase the adhesive force between the resin component and the sheet to form a part of the molded article.

It is further preferable that the adhesive layer formed using the acrylic complex syrup has the same refractive index as the acrylate sheet or a difference of 0.005 or less. In this case, the transparency of the laminated molded article does not differ from the transparency of the sheet, and even if the refractive index according to the temperature changes, the transparency maintains an optically uniform state.

Hereinafter, the production steps of the acrylate syrup, the sheet production step and the acrylate transparent laminated molded article of the present invention will be described in detail.

The present invention can be produced by the following steps.

(1) Preparation of acrylate-based syrup

(2) Production step of acrylate-based sheet

(3) Production of acrylate based transparent laminated molded article

First, the production steps of an acrylate-based syrup and a complex syrup will be described.

In the present invention, a syrup can be prepared by adding additional components such as a monomer, a low-temperature initiator and, if necessary, a crosslinking agent, a molecular weight modifier, a polymerization inhibitor and a crosslinking agent.

A small amount of a polymerization initiator is mixed and mixed in the (meth) acrylic monomer composition so that there is almost no residual initiator, and the mixture is bulk-polymerized at a constant temperature for a certain time until a desired degree of polymerization is obtained. The administration method may be a batch or separate administration method.

The acrylic monomer of the present invention may be a monomer as an acrylic monomer or a mixture of an acrylic monomer containing 50% by weight or more of an acrylic monomer as an acrylic monomer. The acrylic monomer is not particularly limited as far as the acrylic syrup can be produced in the present invention. An acrylic monomer of the invention are the acrylic or methacrylic acid or the formula CH2 = C (R) as an acrylic acid or methacrylic acid having ₂ COOR, R is H, methyl or n- butyl, in particular methyl and n- butyl, R2 Is an optionally substituted hydrocarbyl (e. G., Optionally, halo or hydroxy substituted hydrocarbyl), especially C1-8-alkyl, C6-10-cycloalkyl or C6-10-aryl group. Specific examples of such monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, isobornyl Vinyl esters of acrylic acid and methacrylic acid such as methacrylate, benzyl methacrylate, phenyl methacrylate and isobornyl acrylate, and acrylic acid and methacrylic acid such as hydroxyethyl methacrylate and hydroxypropyl methacrylate ≪ / RTI >

The polymerization initiator of the present invention is not limited as long as it is a low-temperature decomposition initiator. Examples of the polymerization initiator include di-t-butyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide, t-butoxychinneodecanate, t-butyl peroxypivalate, jiraurofaquicide, dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, 1,1-bis (t- butylperoxy) -3,3,5 Organic peroxides such as trimethylcyclohexane and 1,1-bis (t-butylperoxy) cyclohexane, and organic peroxides such as azobisisobutyronitrile, azobisisobalonitrile, 1,1-azobis (1-cyclohexanecarbonyl Azobis-4-methoxy-2,4-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azo Bis-2-methylbutyronitrile, and the like can be used alone or in admixture.

In preparing the syrup of the present invention, a molecular weight regulator may be added. For example, one or more chain transfer agents such as alkylmercaptans, dimethylacetamide, dimethylformamide, and triethylamine may be used. From the viewpoint of handling property and stability, alkyl mercaptans are suitably used and n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, n- Octadecyl mercaptan, 2-ethylhexyl thioglycolate, ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate), and pentaerythritol tetrakis (thioglycolate).

In the present invention, the content of the molecular weight modifier may be suitably used as needed. For example, in order to obtain a polymer having a weight average molecular weight of 50,000 to 400,000 in syrup, the content is preferably 0.08 to 0.2% by weight based on the total weight of the monomers. It does not.

Polymerization inhibitors include hydroquinone, 4-methoxyphenol, or methylhydroquinone, which can stop the radical transfer reaction.

In addition, the polymerization conditions can be controlled to control the viscosity and the polymerization conversion rate. In order to eliminate the rapid reaction heat and to terminate the polymerization, the reaction rate is slowed before and after the maximum reaction temperature using cooling water, Drop it. Nitrogen, which is an inert gas, is injected during the reaction to prevent the polymerization by oxygen, and the heat source can be shut off during heat generation through the precise temperature controller.

In the present invention, the acrylate-based syrup is not limited as far as the conversion of the polymer composition is 5 to 50% by weight, and more preferably 10 to 30% by weight.

The following steps for producing an acrylate-based sheet will be described.

In the production of the acrylate-based sheet of the present invention, in the production of the acrylate-based sheet from the acrylate-based syrup, in order to maintain the inherent characteristics after the bulk polymerization, the heat generation during polymerization is kept constant, Should be adjusted.

For this purpose, molding is carried out by providing spacers between two glass plate molds, mixing a small amount of a low temperature thermal polymerization initiator in the prepared acrylate syrup with little residual initiator, and optionally adding a crosslinking agent, ultraviolet stabilizer thermal stabilizer, , And then the bulk syrup is poured in a large temperature bath or a hot air drier for a certain time.

The glass plate is removed and heat treatment is performed for a predetermined time at a temperature slightly lower than the Tg of the polymer, and the temperature is slowly lowered to room temperature to produce an acrylate-based sheet. To adjust the viscosity and polymerization conversion rate, components such as chain transfer agent may be added, and polymerization inhibitors may be used during polymerization to terminate the abrupt reaction heat removal and polymerization.

As the polymerization initiator to be used in the production of the sheet of the present invention, in particular, a low-temperature initiator may be quercuminoperoxineodecanoate, di-isopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate , Di- (2-ethylhexyl) peroxydicarbonate, di- (3-ethoxyethyl) peroxydicarbonate, di- (methoxyisopropyl) peroxydicarbonate, -Methyl-3-methoxybutyl) peroxydicarbonate, t-butyl peroxyneodecanoate, di-allyl peroxydicarbonate, and di-methallyl peroxydicarbonate, and organic peroxides such as 2,2'- The use of azo compounds such as 2,4-dimethylvaleronitrile alone or a mixture of two or more thereof can prevent local thermal accumulation due to non-uniform polymerization during the polymerization step, thereby preventing the formation of bubbles and gel It is better.

The polymerization initiator may be used alone as the polymerization initiator in the sheet production step of the present invention. Alternatively, the polymerization initiator may be used in combination with a low-temperature polymerization initiator having a half-life of 60 ° C or less for 7 hours or less and a high- It is better to use it. Generally, it is preferable to use 0.02 to 0.1 part by weight of the low-temperature polymerization initiator and 0.01 part by weight or less of the high-temperature polymerization initiator per 100 parts by weight of the total composition.

In the present invention, a crosslinking agent may be used if necessary. Examples of the crosslinking agent include divinylbenzene, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, A mixture of at least one member selected from the group consisting of 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate and pentaerythritol tetraacrylate can be used, But it is preferable to use 0.1 to 2 parts by weight based on 100 parts by weight of the acrylate resin component.

In the present invention, if necessary, a benzotriazole-based compound such as hydroxy t-octylphenylbenzotriazole, hydroxymethylphenylbenzotriazole, or di-t-butylhydroxyphenyl chlorobenzotriazole may be used as the ultraviolet stabilizer And the content thereof is preferably 0.05 to 1 part by weight based on 100 parts by weight of the acrylate resin component.

In one embodiment of the present invention, the spacer may be made of one or more selected from soft PVC, polyester, silicone, nylon, teflon, polyisobutylene, ethylenic copolymer rubber and the like.

The following describes the manufacturing steps of the acrylic laminated molded article.

The acrylate-based laminated molded article of the present invention is obtained by joining an acrylate-based sheet to the acrylate-based syrup of the present invention to form a plurality of laminated bodies including an acrylic sheet / adhesive layer / acrylic sheet structure.

The thickness of the adhesive layer formed by the acrylate composite syrup contained between the acrylate-based sheets of the present invention is not particularly limited, but is preferably 0.1 to 10 mm, preferably 1 to 5 mm, for example.

If the thickness of the adhesive layer is less than 0.1 mm, it is difficult to inject or bubble out of the bubbles due to the surface tension of the acrylate resin. On the other hand, when the thickness of the adhesive layer exceeds 10 mm, It is not easy and contraction may occur.

Therefore, it is necessary to keep the heat generation constant during bulk polymerization so that a stable bonded body is formed, and the influence of external environment should be controlled. To this end, a dam was provided between the surfaces of the two sheets of acrylic sheets and between the four sides of the sides of the acrylic sheet, and a low-temperature thermal polymerization initiator was mixed with the prepared acrylate syrup so as to have almost no residual initiator 0.01 to 1.0 part by weight of a crosslinking agent and 0.01 to 2.0 parts by weight of a UV stabilizer are mixed and subjected to low temperature bulk polymerization and then heat treatment is performed at a temperature slightly lower than Tg for a predetermined time, Thereby forming a rate-based shaped body. At this time, the refractive index of the acrylate-based resin is controlled to be equal to or less than +/- 0.005 of the acrylate-based sheet.

Examples of the polymerization initiator include t-butyl perbenzoate, t-butyl peroxide, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-butyl peroxy 2-ethylhexanoate, Organic peroxides such as peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile Can be used.

The polymerization initiator may be used alone, but it is more preferable to use the polymerization initiator in combination with a low-temperature polymerization initiator having a half-life period of not more than 7 hours at 60 DEG C and a high-temperature polymerization initiator at 80 DEG C for about 7 to 8 hours. Generally, it is preferable to use 0.02 to 0.1 part by weight of the low-temperature polymerization initiator and 0.01 part by weight or less of the high-temperature polymerization initiator per 100 parts by weight of the total composition.

Examples of the crosslinking agent include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol Diethyl acrylate, diacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, and the like may be used alone or in combination, and it is preferable to use 0.1 to 2 parts by weight based on 100 parts by weight of the acrylate resin component.

Examples of the ultraviolet stabilizer include benzotriazole-based compounds such as hydroxy t-octylphenylbenzotriazole, hydroxymethylphenylbenzotriazole and di-t-butylhydroxyphenyl chlorobenzotriazole, 0.05 to 1 part by weight based on 100 parts by weight of the rate-based resin component is preferably used.

As the spacer material, an acrylate-based sheet, a polycarbonate-based sheet, a soft PVC-based sheet, a polyester-based sheet, a nylon-based sheet or a propylene-based sheet can be used. The thickness of the sheet is not limited, but is preferably 2 to 4 mm. If the thickness is less than 2 mm, a smooth surface can not be obtained due to deformation due to shrinkage during polymerization. In order to produce a product having better smoothness, a sheet having a high modulus of elasticity was polymerized as a support.

By controlling the heat generated by the low-temperature initiator in the production of a molded article, it is possible to manufacture an acrylate-based molded article having a stable molded article shape and excellent transmittance, hardness and strength.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

[Example 1]

1) Preparation of syrup

A 1000 ml four-necked flask equipped with a nitrogen gas inlet tube, a cooling water line, a thermometer and a stirrer was placed in a temperature-adjustable oil bath, 300 g of methyl methacrylate and 0.06 g of lauryl peroxide were added, For 85 hours. As a result, it was measured by the following analytical method, and as a result, the conversion was 13.1% by weight, the viscosity was 2476 cps, the weight average molecular weight; And a polydispersity of 2.31 was prepared. The amount of the residual initiator is 10 ppm or less, and the initiating action is not performed at room temperature, so that the storage stability is stable.

(1) Conversion ratio of the prepolymerized polymer: The polymer was sampled from the reactor and dissolved in the solvent. The polymer was separated by the reprecipitation method and dried to measure the solid content.

(2) Viscosity: The viscosity was measured using a Brookfield viscometer DV3 Ultra. The spindle used is no. 14, torque was maintained at 70 ~ 90% and the measurement was done for 2 minutes. ≪ / RTI >

(3) Molecular weight, molecular weight distribution: The molecular weight (weight average molecular weight Mw, number average molecular weight Mn) was measured by gel permeation chromatography (Agilent HPLC 1260). The measurement conditions were THF as the mobile phase, the flow rate was 1.0 ml / min, the column used was MIXED-D manufactured by PLgel, the temperature was 30 ° C, the sample concentration was 0.3 wt% and the injection amount was 25 μL. The detector uses a differential refractometer. The determination of each molecular weight was carried out by preparing a calibration curve by standard polystyrene (molecular weight 69,650, 217,900, 465,600) for GPC manufactured by Agilent.

2) Production of acrylic sheet and acrylic transparent laminated molded article

0.01 part by weight of ADVN (2,2'-Azobis (2,4-dimethyl) valeronitrile) was added to 100 parts by weight of the syrup obtained above and stirred to prepare a complex syrup, And allowed to stand in an oven at 40 DEG C for 15 hours to cast an acrylic sheet having a thickness of 3 mm. The acrylic sheet thus produced was free from air bubbles, was transparent, and had a very smooth surface.

Two or more sheets of acrylate sheets each having a width of 200 mm, a length of 200 mm, and a thickness of 3 mm obtained in the above manner were arranged in a plane at intervals of 3 mm, cells were formed, and peripheral portions except for the injection port were sealed and clamped. The acrylic complex syrup thus prepared was charged and sealed in an injection port, and bulk polymerization was carried out in a thermostatic chamber (or a reflux dryer) under the same conditions as those of the above sheet. The polymerization time (minutes) was defined as the time when no pin of 0.5 mm diameter entered the polymer between the soda glass plates.

After the polymerization, the bonded product obtained an integrated acrylic molded article having a size of 403 mm in length x 403 mm in length x 9 mm in thickness, no flow mark was observed at the interface, and excellent transparency was observed, and bubbles or optically different characteristics We could not observe the part. The appearance of the molded body was visually observed to confirm that it was colorless transparent and uniform.

[Example 2]

An acrylate resin was obtained in the same manner as in Example 1 except that the methyl methacrylate monomer was changed to 90 wt% of methyl methacrylate monomer and 10 wt% of acrylic acid. As a result of evaluating the properties, it was not different from Example 1, Or the flow mark of the interface was not observed.

[Comparative Example 1]

In Example 1, 0.02 g of lauryl peroxide was mixed with 100 parts by weight of methyl methacrylate without using acrylic syrup, and the mixture was placed between two sheets of acrylic sheets prepared in Example 1, and the mixture was stirred at 71 ° C for 393 minutes And the adhesive layer was formed to have a thickness of 3 mm by casting. As a result, bubbles were observed inside the adhesive layer, and local gel was observed.

[Comparative Example 2]

The surface of the sheet prepared in Example 1 was dissolved in chloroform and adhered. At this time, it was found that the flow mark of the bonding surface was observed at the interface, and the bubbles at the interface were also observed.

Claims (10)

Preparing an acrylic syrup by partial addition of an acrylate monomer,
An acrylic-based complex syrup preparation step comprising an initiator in an acrylic syrup, and
Adding the complex syrup between acrylic sheets and casting to form an adhesive layer to produce an acrylic laminated molded article,
Based on the total weight of the acrylic transparent laminated molded article. The method according to claim 1,
Wherein the acrylic-based sheet is produced by casting the acrylic-based complex syrup. The method according to claim 1,
Wherein the acrylic syrup contains 0.005 to 1 part by weight of a radical initiator having a half-life temperature of 50 to 80 DEG C for 10 hours with respect to 100 parts by weight of the acrylic monomer. The method according to claim 1,
Wherein the acrylic syrup has a polymerization conversion ratio of 5 to 50% by weight of the acrylic monomer. 5. The method of claim 4,
The acrylic syrup has a viscosity of 2,000 to 4,000 cps, a weight average molecular weight (Mw) and a number average molecular weight of 600,000 to 800,000 and 150,000 to 350,000, respectively, and the relationship between the weight average molecular weight and the number average molecular weight is Mw / Mn = 2.0 to 3.5 Based transparent laminated molded article. The method according to claim 1,
Wherein the acrylic syrup is produced by bulk polymerization. The method according to claim 6,
Wherein the bonding layer for forming the sheet and for bonding the sheet to the sheet is formed by casting. The method according to claim 1,
Wherein the difference in refractive index between the sheet and the adhesive layer in the transparent laminated formed article is 0.005 or less. The method according to claim 1,
Wherein the composite syrup further comprises at least one selected from a crosslinking agent, a polymerization inhibitor, a polymerization regulator, an ultraviolet ray inhibitor, and a heat stabilizer. Acrylate monomers so as to have a conversion ratio of 10 to 30% by weight to prepare an acrylic syrup;
An acrylic-based complex syrup preparation step comprising an initiator in an acrylic syrup, and
Preparing an acrylic laminated molded article including a laminated structure of an acrylic sheet, an adhesive layer, and an acrylic sheet by injecting the complex syrup between the acrylic sheets and casting the same to form an adhesive layer;
Based on the total weight of the acrylic transparent laminated molded article.