KR20160118735A - The acrylic resin sheet and method for thereof - Google Patents

The acrylic resin sheet and method for thereof Download PDF

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KR20160118735A
KR20160118735A KR1020150047313A KR20150047313A KR20160118735A KR 20160118735 A KR20160118735 A KR 20160118735A KR 1020150047313 A KR1020150047313 A KR 1020150047313A KR 20150047313 A KR20150047313 A KR 20150047313A KR 20160118735 A KR20160118735 A KR 20160118735A
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acrylic resin
sheet
ultraviolet
pressing roll
solution
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KR1020150047313A
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KR101671495B1 (en
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조성일
김지안
전웅식
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김지안
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/24—Thermosetting resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin sheet and a method of manufacturing the same, and more particularly, Applying the prepared acrylic resin solution to an upper end of a glass mold on an endless belt having a glass mold to form a sheet-shaped acrylic resin; Forming an acrylic resin laminate by disposing an ultraviolet transparent film on the sheet-shaped acrylic resin; Passing the acrylic resin laminate through the upper surface pressing roll and the lower surface pressing roll of a roller including an upper surface pressing roll and a lower surface pressing roll to adjust the thickness of the acrylic resin laminate; A primary curing step of curing the sheet-shaped acrylic resin by irradiating ultraviolet rays onto the ultraviolet transmitting film side of the acrylic resin laminate having the thickness adjusted; And a secondary curing step of thermally curing the primary cured acrylic resin in a sheet form.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an acrylic resin sheet,

The present invention relates to an acrylic resin sheet and a method of manufacturing the same. More particularly, the present invention relates to an acrylic resin sheet and a method of manufacturing the same. More particularly, the present invention relates to an acrylic resin sheet, An acrylic resin sheet having a uniform thickness and excellent physical properties, which is prepared by passing through between two rolls whose intervals are adjusted and then performing primary ultraviolet curing and further performing secondary thermosetting, ≪ / RTI >

In the case of products produced by using an acrylic resin material, it generally exhibits excellent physical properties such as weather resistance, scratch resistance, high transparency and light resistance, and excellent balance of mechanical strength and formability. Thus, , Electric and electronic industries, and the like.

Among the acrylic resins, poly (methylmethacrylate) (PMMA) resin is required to be easy to process, light in weight and economical in manufacturing process cost, and in addition, its excellent transparency makes it possible to obtain a sheet- And is widely used in various industrial fields as a substitute for glass.

Such a sheet-like PMMA sheet can be produced by various manufacturing methods such as a cell casting method and a continuous casting method by using methylmethacrylate (MMA) monomer as a main component, or by using PMMA The resin is produced by extrusion or injection molding.

In general, a PMMA sheet using a cell casting method is produced by injecting a batch in which a hardener such as AIBN (Azobisisobutyronitrile) is added to a MMA (methyl methacrylate) monomer, between two glass molds having a uniform thickness, After the curing reaction, the glass mold is separated and prepared. The cell casting method is a vertical casting method in which a glass mold is vertically cured and a horizontal casting method in which the casting is horizontally laid and cured. In general, a PMMA sheet produced by a horizontal casting method has a physical The properties show better characteristics.

However, in the case of the PMMA sheet produced by the above-mentioned method, the lightweight and impact resistance are superior to glass, but the impact resistance is insufficient as compared with other plastic materials, so that the PMMA sheet can be easily broken There is a disadvantage. As a result, the thickness of the PMMA sheet is increased or used only for limited use.

In the case of the conventional cell casting method, two heavy glass molds are used, and a gasket is provided between the two glass molds to form a predetermined gap, and acrylic resin is injected into the gap. However, There has been a problem that it is difficult to produce a PMMA sheet having excellent thickness uniformity due to deformation, thickness variation of a gasket, and change in elastic modulus, or a sheet is shrunk in the process of producing a PMMA sheet. In addition, since the polymerization reaction proceeds one by one, the production efficiency of the PMMA sheet deteriorates. In addition to the cell casting method, in the case of the PMMA sheet produced by the extrusion type or the continuous casting method, And the heat-resistant temperature is also low, so that the application field is limited, and it has been difficult to apply it to various fields.

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an acrylic resin sheet having improved thickness uniformity by using a thickness controlling roll and maximize the molecular weight of an acrylic sheet produced through a photo- And an object of the present invention is to provide an acrylic resin sheet having remarkably improved mechanical strength and heat resistance temperature and a method of manufacturing the same.

In order to achieve the above-mentioned object, the present invention provides a method for producing an acrylic resin solution, Applying the prepared acrylic resin solution to an upper end of a glass mold on an endless belt having a glass mold to form a sheet-shaped acrylic resin; Forming an acrylic resin laminate by disposing an ultraviolet transparent film or an ultraviolet transparent glass on the sheet-shaped acrylic resin; Passing the acrylic resin laminate through the upper surface pressing roll and the lower surface pressing roll of a roller including an upper surface pressing roll and a lower surface pressing roll to adjust the thickness of the acrylic resin laminate; A primary curing step of curing the sheet-shaped acrylic resin by irradiating ultraviolet rays onto the ultraviolet transmitting film side of the acrylic resin laminate having the thickness adjusted; And a secondary curing step of thermally curing the primary cured acrylic resin in a sheet form.

Preferably, the acrylic resin solution comprises a first polymerizable solution comprising an acrylate monomer, a releasing agent, a crosslinking agent and a thermal polymerization initiator; And a second polymerizable solution comprising an aliphatic urethane acrylate oligomer, a polyfunctional acrylic monomer and a photopolymerization initiator; . ≪ / RTI >

Also, preferably, the first polymerizable solution may have a viscosity of 10,000 cP to 30,000 cP.

Further, preferably, the first polymerizable solution may be in a state of being hardened by heat.

Preferably, the acrylic resin solution may have a viscosity of 5,000 cP to 20,000 cP.

Further, preferably, the ultraviolet-transmissive film may have a glass transition temperature of 50 ° C to 300 ° C.

Further, preferably, the ultraviolet-transmitting film may have a thickness of 50 to 500 um.

Preferably, the ultraviolet-transmitting film may have a surface roughness (Ra) of 0.1 to 10 nm on the surface in contact with the sheet-like acrylic resin.

Further, preferably, the primary curing step may be carried out at a temperature of 20 to 50 ° C.

Further, preferably, the ultraviolet ray may have a wavelength of 300 to 365 nm.

Further, preferably, the exposure dose of the ultraviolet ray may be 10 to 5000 mJ / cm 2.

Further, preferably, the secondary curing step may be performed at a temperature of 90 to 150 ° C.

Further, preferably, the secondary curing step may be performed for 1 to 10 hours.

An acrylic resin sheet comprising an acrylic polymer according to the production method of the present invention is provided.

Preferably, the acrylic polymer may have a weight average molecular weight of 1,500,000 to 3,000,000.

The acrylic resin sheet having a uniform thickness can be manufactured due to the manufacturing method feature of passing the space between the two rolls according to the present invention, and the thickness of the acrylic resin sheet can be easily adjusted by the user.

In addition, since no clamp, gasket, heavy glass mold or the like conventionally used in the production of the acrylic resin sheet is used, the production time of the acrylic resin sheet can be shortened, and productivity and manufacturing cost can be reduced.

In addition, it is possible to maximize the molecular weight of the acrylic resin sheet through the photo-curing treatment and the heat-hardening treatment, and thereby it is possible to produce an acrylic resin sheet having excellent mechanical properties and high heat- There is an effect.

1 is a schematic side view of an example of a manufacturing apparatus to which an acrylic resin sheet having a uniform thickness is applied according to an embodiment of the present invention.
2 is a flowchart illustrating a method of manufacturing an acrylic resin sheet having a uniform thickness according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.

However, it is to be understood that the present invention may be embodied with various changes and modifications, and the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

It is also to be understood that the words or words used in the present specification and claims are not intended to be limiting or to be construed in a conventional or dictionary sense and that the inventor shall, It should be construed as meaning and concept consistent with the technical idea of the present invention based on the principle that the concept can be properly defined.

In the following detailed description, the names of the components are divided into the first and second parts for the purpose of easily distinguishing the components, and are not necessarily limited to those in the following description.

Therefore, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention, and they do not represent all the technical ideas of the present invention. Therefore, It should be understood that various changes and modifications may be made.

Hereinafter, the acrylic resin sheet according to the present invention and its manufacturing method will be described in detail.

1 is a schematic side view of an example of a manufacturing apparatus to which an acrylic resin sheet manufacturing method according to an embodiment of the present invention is applied.

1, an apparatus for producing an acrylic resin sheet mainly comprises a supply die 2, an endless belt 3, a main roll 4, a glass mold 5, an ultraviolet transmitting film 6, an upper surface pressing roll 7 A lower pressing roll 8, a light irradiation device 9, a heating mechanism (not shown), an oven 10, and the like.

2 is a flowchart illustrating a method of manufacturing an acrylic resin sheet according to an embodiment of the present invention.

A method for producing an acrylic resin sheet according to an embodiment of the present invention includes the steps of: preparing an acrylic resin solution; Applying the prepared acrylic resin solution to an upper end of a glass mold on an endless belt on which a glass mold is disposed to form an acrylic resin sheet; Forming an acrylic resin laminate by disposing an ultraviolet transparent film or an ultraviolet transparent glass on the sheet-shaped acrylic resin; Passing the acrylic resin laminate through the upper surface pressing roll and the lower surface pressing roll of a roller including an upper surface pressing roll and a lower surface pressing roll to adjust the thickness of the acrylic resin laminate; A primary curing step of curing the sheet-shaped acrylic resin by irradiating ultraviolet rays onto the ultraviolet transmitting film side of the acrylic resin laminate having the thickness adjusted; And a secondary curing step of thermally curing the primary cured acrylic resin in a sheet form.

Referring to FIG. 2, the first polymerizable solution may include an acrylate monomer, a releasing agent, a crosslinking agent, and a thermal polymerization initiator, and the first polymerizable solution is prepared by thermal polymerization.

The first polymerizable solution may comprise 93 to 99.7 wt% of an acrylate monomer, 0.1 to 2 wt% of a release agent, 0.1 to 2 wt% of a crosslinking agent, and 0.1 to 3 wt% of a thermal polymerization initiator.

The acrylate monomer in the first polymerizable solution composition is not particularly limited, but may be selected from the group consisting of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl Alkyl methacrylates such as methacrylate and benzyl methacrylate can be used and alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate can be exemplified as monomers, And at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid and itaconic acid may be further added. In addition to the monomer, an unsaturated carboxylic acid such as acrylic acid, Itaconic anhydride and the like can be further added, and N-phenylmaleimide, N-cyclohexyl A maleimide derivative such as maleimide or Nt-butyl maleimide can be further added, and a maleimide derivative such as 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, A monomer can be further added and a nitrogen-containing monomer such as (meth) acrylamide, (meth) acrylonitrile, diacetone acrylamide, dimethylaminoethyl methacrylate and the like can be further added, and allyl glycidyl An epoxy group-containing monomer such as ether, glycidyl acrylate or glycidyl methacrylate can be further added, and styrene-based monomers such as styrene and -methylstyrene can be further added. One or more of them may be selected and added.

If a plurality of the above-mentioned acrylate monomers are selected and used, it is preferable to use methyl methacrylate as a composition of the first polymerizable solution at a blending ratio of 60% by weight or more.

The release agent of the first polymerizable solution composition is used for the purpose of allowing the acrylic resin sheet produced by the production method of the present invention to be easily peeled off from the glass mold 5 and the ultraviolet transparent film 6. [

The releasing agent is not particularly limited, but a silicone type releasing agent such as cyclohexasiloxane can be used.

The content of the releasing agent is preferably in the range of 0.1 to 2% by weight in the first polymerizable solution. When the releasing agent is mixed at less than 0.1% by weight, the acrylic resin sheet is mixed with the glass mold 5 and ultraviolet It may not be easily peeled off from the transparent film. If the content is more than 2% by weight, the surface tension of the acrylic resin sheet produced by the production method of the present invention may be lowered, which may adversely affect adhesion during hard coating.

The crosslinking agent in the first polymerizable solution composition is a component for bonding chains of the acrylate monomer to be polymerized, thereby improving the heat resistance of the acrylic resin sheet.

The crosslinking agent is not particularly limited in its kind, but is preferably a crosslinking agent such as ethylene glycol diacrylate, allyl acrylate, ethylene glycol dimethacrylate, allyl methacrylate, divinylbenzene, trimethylolpropane triacrylate, Triallyl cyanate, 1,4-butanediol dimethacrylate, butylene glycol dimethacrylate, 2,4-toluene diisocyanate, and the like, and at least one selected from the group consisting of can do.

The content of the crosslinking agent is preferably in a range of 0.1 to 2% by weight in the first polymerizable solution. When the crosslinking agent is mixed at less than 0.1% by weight, the crosslinking reaction between the acrylate chains may be insufficient The improvement of the heat resistance of the acrylic resin sheet of the present invention can not be expected. If the acrylic resin sheet of the present invention is blended at 2% by weight or more, there is a problem that the acrylic resin sheet produced by the production method of the present invention is deteriorated.

The thermal polymerization initiator in the first polymerizable solution composition is a component capable of generating radicals by heat.

The thermal polymerization initiator is not particularly limited in its kind but is preferably selected from the group consisting of benzoyl peroxide, acetyl peroxide, hydrogensperoxide, di-tertiary butyl peroxide, diaryl peroxide, cumyl hydroperoxide, azobisisole Potassium nitrate, potassium nitrate, potassium nitrate, potassium nitrate, potassium nitrate, and potassium sulfate.

The content of the thermal polymerization initiator is preferably in a range of 0.1 to 3% by weight in the first polymerizable solution. When the thermal polymerization initiator is mixed in an amount of less than 0.1% by weight, the amount of the thermal polymerization initiator is insufficient, The reaction time may be prolonged and the processability may be deteriorated or the reaction polymerization may not be carried out sometimes. In case of mixing at 3 wt% or more, the reaction polymerization time may be shortened However, since the average molecular weight of the resulting acrylate polymer is lowered and the molecular weight distribution is widened, it is difficult to expect consistent physical properties of the acrylic resin sheet according to the production method of the present invention.

Here, the process of preparing the first polymerizable solution using the composition of the first polymerizable solution or the like may be performed by raising the temperature of the acrylic monomer to 20 to 40 ° C, adding the thermal polymerization initiator And then the temperature was raised to 40 to 60 ° C. Then, the releasing agent and the crosslinking agent were added to each other, and the temperature of the reactant was continuously increased to reach 80 to 100 ° C., And terminating the reaction when the molecular weight range is approximately 100,000 to 500,000.

It is preferable that the first polymerizable solution finally has a molecular weight of 100,000 to 500,000. If the molecular weight of the first polymerizable solution is less than the above range, the effect of improving the hardness, durability and heat resistance of the acrylic resin sheet to be produced can not be expected. If the molecular weight exceeds the molecular weight range, the flexibility of the acrylic resin sheet May occur.

It is also preferable that the first polymerizable solution has a viscosity of 10,000 cP to 30,000 cP. If the viscosity of the first polymerizable solution is less than the above-mentioned viscosity range, in the process of producing the acrylic resin sheet using the acrylic resin solution containing the first polymerizable solution, the acrylic resin solution flows out of the glass mold If the viscosity range is exceeded, it is difficult to uniformly apply the acrylic resin solution in the form of a sheet, the moldability and the like may be reduced and the thickness control may not be easy, and the appearance of the sheet may be deteriorated.

Next, referring to FIG. 2, the second polymerizable solution may include an aliphatic urethane acrylate oligomer, a polyfunctional acrylic monomer, and a photopolymerization initiator, and they are mixed to prepare a second polymerizable solution (S102).

The second polymerizable solution may contain 30 to 60 wt% of an ultraviolet curing type aliphatic urethane acrylate monomer, 30 to 60 wt% of a polyfunctional acrylic monomer, and 0.001 to 5 wt% of a photopolymerization initiator.

The second polymerizable solution is contained in the acrylic resin sheet of the present invention in the role of an ultraviolet curable resin. The second polymerizable solution is prepared by mixing an oligomer having an ultraviolet ray reactor and a multi-functional acrylic monomer with ultraviolet The acrylic resin sheet of the present invention has an excellent optical and mechanical properties while having heat resistance and chemical stability.

Of the second polymerizable solution composition, the UV-curable aliphatic urethane acrylate oligomer is not particularly limited, but tetramethylene diisocyanate, hexamethylene diisocyanate, and the like are exemplified, and 1 Or more species.

The content of the ultraviolet-curable aliphatic urethane acrylate oligomer is preferably used in a range of 30 to 60% by weight in the second polymerizable solution.

The polyfunctional acrylic monomer in the second polymerizable solution composition is not particularly limited, but is preferably selected from the group consisting of pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol acrylate, trimethylolpropane tri Acrylate, and the like, and may include at least one selected from the group consisting of these.

The content of the polyfunctional acrylic monomer is preferably used in a range of 30 to 60% by weight in the second polymerizable solution.

In the second polymerizable solution composition, the photopolymerization initiator is a component capable of generating radicals in response to a predetermined light.

Examples of the photopolymerization initiator include, but are not limited to, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, and triazine-based compounds, Benzophenone, 4-phenylbenzophenone, methylbenzoylformate, hydroxydimethylacetophenone, benzyl dimethyl ketal, ethyl-4-dimethylaminobenzoate, and the like. have.

The content of the photopolymerization initiator is preferably used in a range of 0.001 to 5 wt% in the second polymerizable solution. When the photopolymerization initiator is mixed in an amount of less than 0.001 wt%, the ultraviolet curable aliphatic urethane The yield of conversion of the acrylate oligomer and the polyfunctional acrylic monomer into the polymer particles may be lowered so that the reaction polymerization time may be prolonged to lower the processability and sometimes the reaction polymerization may not be carried out. When the polymerization initiator is mixed in an amount of 5% by weight or more, the acrylic resin sheet produced according to the production method of the present invention may have poor optical performance and weather resistance due to the unreacted material of the photopolymerization initiator.

Referring to FIG. 2, the acrylic resin solution 1 is prepared by mixing the first polymerizable solution and the second polymerizable solution (S103).

Here, the acrylic resin solution (1) preferably has a viscosity of 5,000 cP to 20,000 cP. If the viscosity of the acrylic resin solution is less than the above viscosity range, there may occur a problem that the acrylic resin solution flows out of the glass mold due to a low viscosity in the process of producing the acrylic resin sheet. If the viscosity exceeds the viscosity range, It is difficult to uniformly apply the acrylic resin solution to the mold in the form of a sheet, the moldability and the like are deteriorated, the thickness control is not easy, and the appearance of the sheet is deteriorated.

Next, referring to FIG. 2 showing a manufacturing apparatus to which an acrylic resin sheet manufacturing method according to an embodiment of the present invention is applied, the acrylic resin solution (1) (S104).

The endless belt 3 of the apparatus for producing an acrylic resin sheet according to the present invention is in a state of being engaged with a plurality of main rolls 4 and while maintaining a predetermined tension by the main roll 4, It may have a structure capable of rotating clockwise or counterclockwise according to a predetermined power of the motor 4.

A glass mold 5 is disposed on the upper surface of the endless belt 3 and a plurality of glass molds 5 may be provided on the endless belt 3 at predetermined intervals.

Here, the acrylic resin solution (1) supplied to the supply die (2) is coated on the upper surface of the glass mold (5) to form a sheet-shaped acrylic resin (S105).

Then, the ultraviolet transparent film 6 or the ultraviolet transparent glass having the same area as the glass mold is coated on the sheet-like acrylic resin, and a glass mold, a sheet-shaped acrylic resin and an ultraviolet transparent film (glass) Thereby forming a stacked acrylic resin laminate (not shown) (S106).

The ultraviolet light transmissive film 6 may be a known film which is not particularly limited in its kind. Typical examples thereof include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polycarbonate (PC) A synthetic resin film such as a polyethylene terephthalate film, a polystyrene (PS) film, a polyamide (Nylon) film, a polyamideimide (PAI) film, a polyethylene (PE) film or a polyvinyl chloride (PVC) film, a cellulose acetate film , Cellophane, glass, and glase. Examples of the film include a film made of one or more selected from the group consisting of these materials, a film made of these materials, or a film obtained by laminating these films in multiple layers. Further, a film layer having a function such as a peeling layer or the like may be further laminated on one side of the ultraviolet-transmitting film 6.

The ultraviolet-transmitting film 6 is preferably a film having a glass transition temperature in the range of 50 to 300 占 폚 and a thickness of 50 to 500 占 퐉, the properties of which are not easily deformed by heat or light.

In order to obtain an effect of smoothly producing the surface appearance of the acrylic resin sheet to be produced, the surface roughness (Ra) of the surface of the ultraviolet transmitting film 6 in contact with the sheet-like acrylic resin may be 0.1 to 10 nm.

Thereafter, the acrylic resin laminate is conveyed in the direction of a heating mechanism (not shown) for regulating the reaction temperature by the endless belt 3, and then controlled by the heating mechanism in an appropriate reaction temperature range of 20 to 50 ° C (S107).

Next, the endless belt 3 is driven to pass the acrylic resin laminate disposed on the endless belt 3 between the rollers including the upper surface pressing roll 7 and the lower surface pressing roll 8, The thickness of the acryl-based resin is adjusted (S108).

More specifically, step S108 of adjusting the thickness of the sheet-shaped acrylic resin is performed. When the endless belt 3 is rotated in one direction through a predetermined power generated by driving the main roll 4, The acrylic resin laminate passes through the upper surface pressing roll 7 and the lower surface pressing roll 8. At this time, the acrylic resin laminate passes through the upper surface pressing roll 7 and the lower pressing roll 8, So that the thickness of the sheet-like acrylic resin is adjusted. Since the interval between the upper surface pressing roll 7 and the lower surface pressing roll 8 can be easily set according to the purpose of the user, the thickness of the acrylic resin sheet of the present invention can be easily adjusted, The manufacturing method effect of the present invention capable of producing a resin sheet is exhibited.

Here, in the known method of producing an acrylic resin sheet, in a cell casting method, each polymerization reaction mixture is placed on two heavy glass substrates so that spacers are opposed so as to form gaps at regular intervals, The reactive mixture is injected, sealed, and the polymerization reaction is carried out to prepare an acrylic resin sheet. At this time, in order to compensate for the shrinkage due to the polymerization reaction, a gasket having elasticity as an encapsulating material is used and a clamp for applying a constant pressure to the glass plate is tightened to produce a sheet. Since the thickness variation and the elastic modulus of the gasket are varied flexibly , It is difficult to control the thickness uniformity of the acrylic resin sheet produced as a result.

However, according to the method for producing an acrylic resin sheet by the apparatus for producing an acrylic resin sheet of the present invention, since a clamp which is conventionally used for fastening a plurality of glass substrates is not used, a predetermined external pressure It is possible to produce a sheet having a uniform thickness, and a heavy glass mold is not used, and the production process efficiency is remarkably improved.

Further, in the continuous cell casting method of the present invention, only one glass mold and one ultraviolet ray transmissive film are used, the uniformity of the thickness of the acrylic resin sheet can be easily maintained without using the additional gasket having elasticity, The cost is significantly reduced.

Further, in the case of the present invention, the acrylic resin laminate is passed between the rollers including the upper surface pressing roll 7 and the lower surface pressing roll 8, which constitute the acrylic resin laminate and whose intervals are adjusted, It is possible to control the thickness of the resulting sheet more easily than in the prior art.

Next, after the sheet-shaped acrylic resin of the temperature-controlled acrylic resin laminate is transferred by the endless belt 3 in the direction of the light irradiation device 9 for photo-curing treatment, the light irradiation device 9 ) Is irradiated with light onto an ultraviolet transparent film disposed on the sheet-like acrylic phase, and the acrylic resin is photo-cured (S109).

The acrylic resin is irradiated with light emitted from the light irradiating device 9 to be photo-cured, so that the appearance of the acrylic resin sheet is provided.

The light emitted from the light irradiation device 9 may include X rays, ultraviolet rays, electron rays, and the like. However, ultraviolet rays having an advantage of easy handling and exhibiting an excellent photo-curing effect of an acrylic resin may be preferable.

As the ultraviolet ray, a known ultraviolet ray irradiation apparatus which does not limit the irradiation apparatus can be used. Typical examples of the ultraviolet ray irradiation include ultraviolet irradiation such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, Devices and the like.

The ultraviolet ray has an exposure amount range of 10 to 5000 mJ / cm 2, and ultraviolet rays having a wavelength range of 300 to 365 nm can be used. If the amount of exposure is less than the above range, the decomposition amount of the photoinitiator may be reduced and the polymerization rate may be delayed. If the amount exceeds the above range, the decomposition amount of the photopolymerization initiator may be excessively increased, There may arise a problem that the molecular weight of the acrylic resin sheet to be produced may be lowered and the yellowing of the acrylic resin sheet produced by the irradiation of excess ultraviolet light may occur.

When the acrylic resin is irradiated with ultraviolet rays in accordance with the condition of the exposure dose of the ultraviolet ray, the radical generation rate of the photopolymerization initiator is increased, and the photopolymerization proceeds rapidly, so that the processing time can be shortened.

Next, the acryl-based resin laminate including the acrylic resin subjected to photo-curing treatment is transferred to an oven 10 for heat-curing (S110).

The acrylic resin laminate, which has been photo-cured and transferred to the oven 10, is thermally cured in response to heat emitted from the oven 10.

The acrylic resin laminate transferred to the oven 10 is thermally cured to produce an acrylic resin sheet having an acrylic polymer having a network structure (S111).

Here, the thermal curing reaction may be performed at a temperature of 90 to 150 ° C for 1 to 10 hours.

If the acrylic resin sheet is subjected to the heat curing treatment within the temperature range of the heat curing treatment temperature and the heat curing treatment time, the additional polymerization reaction of the unreacted monomer remaining in the acrylic resin sheet can be induced. When the unreacted monomer of the acrylic resin sheet is further polymerized, the weight average molecular weight of the acrylic resin sheet may be maximized to maintain a high molecular weight of 1,500,000 to 3,000,000 or more. When the molecular weight of the acrylic resin sheet is maximized, an acrylic resin sheet having excellent mechanical strength, surface hardness and heat resistance temperature of 100 DEG C or more can be produced.

If the temperature of the heat curing treatment is less than the above range, it is difficult to induce an additional reaction of the unreacted monomer, thereby making it difficult to maximize the molecular weight of the acrylic resin sheet. In addition, If it is used in an environment, outgassing phenomenon may occur and heat resistance may be deteriorated. On the other hand, when the temperature of the heat-curing treatment is higher than the above-mentioned range, pinhole phenomenon occurs in which minute cavities of minute gas such as needle are stuck on the surface of the acrylic resin sheet due to rapid boiling of the unreacted monomer, The problem may become inadequate.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the present invention, but rather illustrate the present invention. Should be considered. The scope of the present invention is defined by the appended claims rather than by the description below, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

< Manufacturing example > Production of acrylic resin sheet

The following materials are prepared for the examples.

Acrylate Monomer: Liquid Methyl Methacrylate

Release agent: Cyclohexasiloxane

Crosslinking agent: Ethylene glycol diacrylate

Thermal polymerization initiator: Azobisisobutyronitrile (AIBN)

Aliphatic urethane acrylate oligomer: tetramethylene diisocyanate

Polyfunctional acrylic monomers: pentaerythritol triacrylate

Photopolymerization initiator: Hydroxydimethylacetophenone

1st Polymerizable  Preparation of solution

In order to prepare the first polymerizable solution of the present invention, first, 95% by weight of liquid methyl methacrylate as an acrylate monomer, 1% by weight of cyclohexasiloxane as a mold release agent, 1% by weight of ethylene glycol diacrylate as a crosslinking agent, 3% by weight of azobisisobutyronitrile (AIBN) as an initiator is prepared.

After the liquid methylmethacrylate was heated so as to reach a temperature of 30 ° C, 3% by weight of azobisisobutyronitrile (AIBN) as the thermal polymerization initiator was added when the heating of the liquid methylmethacrylate was completed , And sufficiently heated so that the temperature of the reactant charged with the thermal polymerization initiator reached 50 캜.

At this time, when the temperature of the reaction reached 50 캜, 1% by weight of cyclohexasiloxane as a mold release agent and 1% by weight of ethylene glycol diacrylate as a crosslinking agent were added, and then the temperature of the reaction was continuously increased to 90 캜 The reaction was terminated.

Second Polymerizable  Preparation of solution

First, in order to prepare the second polymerizable solution of the present invention, 49.5% by weight of tetramethylene diisocyanate as an aliphatic urethane acrylate oligomer, 49.5% by weight of pentaerythritol triacrylate as a polyfunctional acrylic monomer, 1% by weight of dimethylacetophenone were prepared and mixed to prepare a second polymerizable solution.

Production of acrylic resin sheet

The acrylic resin solution (1) was prepared by mixing the first polymerizable solution and the second polymerizable solution prepared through the above-described method.

Thereafter, the acrylic resin solution 1 was introduced into the supply die 2 of the acrylic resin sheet production apparatus as shown in Fig. 1, and the acrylic resin solution 1 was placed on the endless belt 3 of stainless steel having a width of 500 mm, The acrylic resin solution (1) was applied to the top of the substrate (5) to prepare a sheet.

Subsequently, an acrylic resin laminate was formed on the upper surface of the sheet-shaped acrylic resin to cover the ultraviolet transmitting film 6 having a width of 500 mm, a thickness of 200 mu m and a surface roughness (Ra) of 5 nm to drive the endless belt 3 And moved at a conveyance speed of 1.5 m / min in the direction of the hot air heating mechanism for controlling the reaction temperature of the acrylic resin laminate to reach the temperature of the acrylic resin laminate to 40 캜.

Next, the acrylic resin laminated body adjusted to a temperature of 40 ° C is passed between the upper surface pressing roll 7 and the lower surface pressing roll 8 spaced apart from each other by a predetermined distance to adjust the thickness of the acrylic resin, An external appearance of the acrylic resin sheet was formed through a light curing treatment step of irradiating ultraviolet rays under the condition of 365 nm wavelength band and an exposure dose of 1000 mJ / cm 2 using a light irradiation device 9 equipped with an ultraviolet LED.

Thereafter, the acrylic-based resin laminate subjected to the photo-curing treatment was transferred to a box oven carriage and thermally cured at 120 ° C for 2 hours. The glass mold of the acrylic resin laminate and the ultraviolet-transmissive film were peeled off to obtain a uniform thickness Based resin sheet.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the exemplary embodiments, but, on the contrary, Therefore, the scope of the present invention is not limited to the embodiments and the accompanying drawings.

1: Acrylic resin solution
2: feed die
3: Endless belt
4: Main roll
5: Glass mold
6: ultraviolet transparent film
7: Top pressing roll
8: Lower press roll
9: Light irradiation device
10: Oven

Claims (15)

Preparing an acrylic resin solution;
Applying the prepared acrylic resin solution to an upper end of a glass mold on an endless belt on which a glass mold is disposed to form an acrylic resin sheet;
Forming an acrylic resin laminate by disposing an ultraviolet transparent film or an ultraviolet transparent glass on the sheet-shaped acrylic resin;
Passing the acrylic resin laminate through the upper surface pressing roll and the lower surface pressing roll of a roller including an upper surface pressing roll and a lower surface pressing roll to adjust the thickness of the acrylic resin laminate;
A primary curing step of curing the sheet-shaped acrylic resin by irradiating ultraviolet light onto the ultraviolet transparent film or ultraviolet transparent glass of the acrylic resin laminate having the thickness adjusted; And
A secondary curing step of curing the primary cured acrylic resin in a sheet form by heat;
Based resin sheet. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 1,
The acrylic resin solution
A first polymerizable solution comprising an acrylate monomer, a releasing agent, a crosslinking agent and a thermal polymerization initiator; And
A second polymerizable solution comprising an aliphatic urethane acrylate oligomer, a polyfunctional acrylic monomer, and a photo polymerization initiator. 3. The method of claim 2,
Wherein the first polymerizable solution has a viscosity of 10,000 cP to 30,000 cP. 3. The method of claim 2,
Wherein the first polymerizable solution is in a state of being hardened by heat. The method according to claim 1,
Wherein the acrylic resin solution has a viscosity of 5,000 cP to 20,000 cP. The method according to claim 1,
Wherein the ultraviolet-transmitting film has a glass transition temperature of 50 ° C to 300 ° C. The method according to claim 1,
Wherein the ultraviolet-transmissive film has a thickness of 50 to 500 mu m. The method according to claim 1,
Wherein the ultraviolet-transmitting film has a surface roughness (Ra) of 0.1 to 10 nm on the surface in contact with the sheet-like acrylic resin. The method according to claim 1,
Wherein the primary curing step is performed at a temperature of 20 to 50 ° C. The method according to claim 1,
Wherein the ultraviolet light has a wavelength of 300 to 365 nm. The method according to claim 1,
Wherein an exposure amount of the ultraviolet ray is 10 to 5000 mJ / cm &lt; 2 &gt;. The method according to claim 1,
Wherein the second curing step is performed at a temperature of 90 to 150 ° C. The method according to claim 1,
Wherein the second curing step is performed for 1 to 10 hours. 14. An acrylic resin sheet comprising an acrylic polymer, which is produced by the method according to any one of claims 1 to 13. 15. The method of claim 14,
Wherein the acrylic polymer has a weight average molecular weight of 1,500,000 to 3,000,000.
KR1020150047313A 2015-04-03 2015-04-03 The acrylic resin sheet and method for thereof KR101671495B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200115906A (en) * 2019-03-29 2020-10-08 한국산업기술시험원 A method for producing a high hardness sheet using a high viscosity acrylic resin, and a method for producing a high hardness sheet

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Publication number Priority date Publication date Assignee Title
KR100505356B1 (en) * 2004-11-26 2005-07-29 신한기연주식회사 Apparatus for manufacturing a acryl sheet
KR20080055056A (en) * 2006-12-14 2008-06-19 미래나노텍(주) Apparatus and method for manufacturing an optical sheet
KR20100114669A (en) * 2009-04-16 2010-10-26 김한슬 The multiple-ability adhesive the board and film which it uses the manufacturing method which sells and that and film board petal
JP2014024880A (en) * 2012-07-24 2014-02-06 Dic Corp Uv-curable urethane acrylate resin composition, thin film molded article, optical film, and production method of thin film molded article

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100505356B1 (en) * 2004-11-26 2005-07-29 신한기연주식회사 Apparatus for manufacturing a acryl sheet
KR20080055056A (en) * 2006-12-14 2008-06-19 미래나노텍(주) Apparatus and method for manufacturing an optical sheet
KR20100114669A (en) * 2009-04-16 2010-10-26 김한슬 The multiple-ability adhesive the board and film which it uses the manufacturing method which sells and that and film board petal
JP2014024880A (en) * 2012-07-24 2014-02-06 Dic Corp Uv-curable urethane acrylate resin composition, thin film molded article, optical film, and production method of thin film molded article

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200115906A (en) * 2019-03-29 2020-10-08 한국산업기술시험원 A method for producing a high hardness sheet using a high viscosity acrylic resin, and a method for producing a high hardness sheet

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