JP2007296711A - Abrasion resistant resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an abrasion resistant resin laminate in which abrasion resistance is improved in a substrate constituted of an acrylic resin containing a hard dispersed phase. <P>SOLUTION: In the abrasion resistant resin laminate 11, a hard coat layer 13 of 1-5 μm thickness is laminated on a substrate layer 12 constituted of the acrylic resin as a thermoplastic matrix resin containing the hard dispersed phase of a thermosetting resin such as a phenol resin, amino resin, epoxy resin, silicone resin, thermosetting polyimide resin, thermosetting polyurethane resin, or the like. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a scratch-resistant resin laminate, and more particularly, to a scratch-resistant resin laminate having improved scratch resistance.

Conventionally, a molded body using the scratch-resistant resin described in Patent Document 1 is known as a resin molded body imparted with scratch resistance on the surface of the molded body to be molded with a thermoplastic resin. Such a scratch-resistant resin has a constitution in which a hard resin obtained by radical polymerization is included as a dispersed phase in a thermoplastic resin which is a matrix resin. Such a dispersed phase improves the scratch resistance of the resin molded body.
JP 2000-336277 A

  However, in the above-described scratch-resistant resin, when an acrylic resin is used as the thermoplastic resin, for example, when it comes into contact with a hard material such as steel wool, the matrix resin portion has a particularly low scratch resistance and is easily scratched. There was a problem.

  On the other hand, a method of laminating a scratch-resistant resin layer composed of an ultraviolet curable resin or the like with a predetermined thickness is generally used to improve the scratch resistance on the surface of a resin molded body using an acrylic resin. . According to this resin laminate, functions such as scratch resistance and abrasion resistance are improved by the laminated scratch-resistant resin layer. However, the scratch-resistant resin layer has a problem that warpage, undulation, peeling, and the like occur as the resin is cured and contracted because the base material made of acrylic resin is different from the resin material.

  Therefore, as a result of intensive studies, the present inventors have determined that the thickness of the scratch-resistant resin layer is set within a predetermined range in a base material composed of an acrylic resin containing a hard dispersed phase, and the resin lamination The inventors have found that the scratch resistance can be improved while preventing warpage and undulation on the surface of the body, and have completed the present invention.

  The present invention has been made in view of such conventional circumstances, and its purpose is to provide a scratch-resistant resin having improved scratch resistance in a substrate composed of an acrylic resin containing a hard dispersed phase. The object is to provide a laminate.

  In order to achieve the above object, an invention according to claim 1 is a scratch-resistant resin having a thickness of 1 to 5 μm on a substrate composed of an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase. It is a scratch-resistant resin laminate in which layers are laminated.

According to a second aspect of the present invention, in the scratch-resistant resin laminate according to the first aspect, the acrylic resin is polymethyl methacrylate.
The invention described in claim 3 is the scratch-resistant resin laminate according to claim 1 or claim 2, wherein the scratch-resistant resin layer is a hard coat layer.

  In the invention according to claim 4, a base material layer composed of an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase is laminated on the surface of the base material composed of an acrylic resin, and It is an abrasion resistant resin laminate in which an abrasion resistant resin layer having a thickness of 1 to 5 μm is laminated on a material layer.

  According to the present invention, scratch resistance can be improved in a base material composed of an acrylic resin containing a hard dispersed phase.

Hereinafter, one embodiment of the scratch-resistant resin laminate embodying the present invention will be described with reference to FIG.
In the scratch-resistant resin laminate 11 of this embodiment, as shown in FIG. 1A, a hard coat layer 13 as a scratch-resistant resin layer is laminated on the front and back surfaces of a base layer 12 as a base. It is constituted by. Further, as shown in FIG. 1B, the hard coat layer 13 may be laminated on the base material layer 12 only on the surface (upper surface). Further, as shown in FIG. 1C, the base material layer 12 may be laminated on the front surface and the back surface of the substrate 14 (molded body), and the hard coat layer 13 may be further laminated on the upper surface thereof.

  The base material layer 12 is made of a thermoplastic matrix resin containing a hard dispersed phase (hereinafter referred to as “hard dispersed phase”). In this embodiment, the thermoplastic matrix resin is an acrylic resin as a thermoplastic resin. The following compounds are mentioned as a monomer used for acrylic resin. For example, methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (Meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopenteni Oxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyl maleate Oxyethyl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meta ) Acrylate, diethylaminoethyl (meth) acrylate and the like. These may be used by polymerizing alone or in combination of two or more. Further, other monomers that can be polymerized with these acrylic monomers, for example, polyolefin monomers, vinyl monomers, and the like may be used in combination.

  The hard dispersed phase is contained and dispersed in the acrylic resin constituting the base layer 12 in order to improve heat resistance or scratch resistance with respect to the base layer 12. The material constituting the hard dispersed phase is not particularly limited as long as it is more excellent in heat resistance or scratch resistance than the acrylic resin, but a thermosetting resin is preferably used.

  Thermosetting resins include phenol resins, amino resins, epoxy resins, silicone resins, thermosetting polyimide resins, thermosetting polyurethane resins, and other polycondensation or addition condensation resins, thermosetting acrylic resins, vinyl Examples include addition polymerization resins such as ester resins, unsaturated polyester resins, and diallyl phthalate resins. You may use a thermosetting resin individually or in combination of 2 or more types. Moreover, you may use combining these thermoplastic resins and the thermoplastic resin which has an unsaturated bond which can be bridge | crosslinked.

  The shape of the hard dispersed phase is not particularly limited, such as particulate, spherical, linear, and fibrous. Spherical shape is preferable because it is easily dispersed uniformly in the acrylic resin which is a thermoplastic matrix resin. The particle size of the hard dispersed phase is appropriately set according to the purpose and application of the scratch-resistant resin laminate 11, but is preferably 0.1 to 1000 μm. Although the compounding quantity in the base material layer 12 of a hard dispersed phase is suitably set according to the intended purpose of the abrasion-resistant resin laminated body 11, an application, etc., Preferably it is 0.1 to 60 weight%.

  Although the method of including a hard dispersed phase in the base material layer 12 is not specifically limited, For example, the following method is mentioned. A thermosetting resin material constituting a hard dispersed phase is added to the acrylic resin material constituting the base material layer 12. Next, after melt-kneading and forming into a predetermined shape, a hard dispersed phase can be formed by causing phase separation and crosslinking. Alternatively, the thermosetting resin may be molded into a particulate form in advance, added to the acrylic resin, and kneaded and molded at a temperature at which the thermosetting resin does not dissolve.

  The hard coat layer 13 is laminated on the substrate layer 12 with a predetermined thickness, thereby improving the scratch resistance of the scratch-resistant resin laminate 11 by a synergistic effect with the substrate layer 12 including the hard dispersed phase. Laminated for. The resin material constituting the hard coat layer 13 is not particularly limited. For example, a solventless ultraviolet curable resin, a solvent type ultraviolet curable resin, an electron beam curable resin, a thermosetting resin, Examples thereof include a photocurable resin and a two-component mixed curable resin. Among these, a solvent-free ultraviolet curable resin is preferable from the viewpoint that a hard coat layer can be easily and efficiently formed, and that facilities for production of a resin laminate can be simplified. .

  As the ultraviolet curable resin, for example, it is preferable to use a resin in which a prepolymer, an oligomer, and a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule are appropriately mixed. Specific examples of the prepolymer and oligomer include acrylates such as urethane acrylate, polyester acrylate, epoxy acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate. , Unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, and cationic polymerization type epoxy compounds.

  Specific examples of the monomer include, for example, styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, and acrylic acid. Acrylic esters such as methoxybutyl and phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate and the like, acrylic Acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N-dimethylamino) ethyl, acrylic acid-2- (N, N-dibenzylamino) methyl, acrylic acid-2- ( N, N-diethylamino) Unsaturated substituted amino alcohol esters such as pills, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, Compounds such as triethylene glycol diacrylate, polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or polythiol having two or more thiol groups in the molecule Compounds such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathiog Examples include recolate and the like. These ultraviolet curable resins may be used alone or in combination of two or more. Conventionally known photopolymerization initiators, photopolymerization accelerators, storage stabilizers and the like are blended with the ultraviolet curable resin.

  The thickness of the hard coat layer 13 is 1 to 5 μm, preferably 1 to 3 μm. If the thickness is less than 1 μm, the effect of improving the scratch resistance may not be obtained. On the other hand, when the thickness exceeds 5 μm, there is a possibility that warpage, undulation, peeling, etc. may occur as the ultraviolet curable resin constituting the hard coat layer is cured and contracted.

  As a method of laminating the hard coat layer 13 on the upper surface of the base material layer 12, a known method is used. For example, laminating method using cover film, dip coating method, natural coating method, reverse coating method, comma coater method, roll coating method, spin coating method, wire bar method, extrusion method, curtain coating method, spray coating method, The gravure coat method etc. are mentioned. In addition, for example, a method of using a transfer sheet in which a hard coat layer is bonded to a release layer and laminating the hard coat layer on one side of the substrate may be employed.

  An example of the substrate 14 shown in FIG. 1C is an acrylic resin that does not contain a hard dispersed phase. As the monomer used for the acrylic resin, the monomers exemplified in the base material layer 12 described above can be used. In order to improve adhesiveness with the base material layer 12 laminated | stacked on the board | substrate 14, it is preferable to use the same kind of monomer as the monomer used in the base material layer 12. FIG.

According to the scratch-resistant laminate of the present embodiment, the following effects can be obtained.
(1) In this embodiment, a hard coat layer 13 is laminated as a scratch-resistant resin having a thickness of 1 to 5 μm on a base material layer 12 composed of an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase. ing. Therefore, the scratch resistance of the laminate can be improved by a synergistic effect with the hard dispersed phase and the hard coat layer having a predetermined thickness.

  (2) Further, since the laminated hard coat layer 13 is 1 to 5 μm, warpage and waviness caused by curing and shrinking of the ultraviolet curable resin constituting the hard coat layer 13, peeling of the hard coat layer, and the like Can be suppressed.

  (3) Moreover, since the hard coat layer 13 to be laminated is 1 to 5 μm, there is no possibility that functions such as transparency exhibited from the base material layer 12 composed of the underlying acrylic resin are deteriorated.

(4) Further, it is not necessary to increase the thickness of the hard coat layer 13 in order to improve the scratch resistance, and the manufacturing cost can be suppressed.
(5) In this embodiment, when the hard coat layer 13 is laminated on the front surface and the back surface of the base material layer 12, warpage and undulation caused by curing and shrinking of an ultraviolet curable resin or the like constituting the hard coat layer 13. Can be further prevented.

  (6) In this embodiment, when the base material layer 12 and the hard coat layer 13 are laminated on the front surface and the back surface of the substrate 14, respectively, the thickness of the scratch-resistant resin laminate is obtained without using a hard dispersed phase. Can be thicker. That is, the scratch-resistant resin laminate can be produced at a lower cost than when the thickness of the scratch-resistant resin laminate is increased only with an acrylic resin containing a hard dispersed phase.

  (7) In addition, the thickness of the base material layer 12 made of an acrylic resin containing a hard dispersed phase can be reduced, and the thickness of the hard coat layer 13 can also be reduced. Therefore, functions such as transparency generated from the acrylic resin constituting the substrate 14 can be secured and improved.

  (8) In this embodiment, when the monomer used in the base material layer 12 and the monomer constituting the substrate 14 are configured in the same type, the adhesiveness with the base material layer 12 laminated on the substrate 14 Can be improved.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
Example 1
Molding a resin composition (OROGLAS HT121, manufactured by Arkema Co., Ltd.) containing poly (methyl methacrylate) (PMMA) as a thermoplastic matrix resin material into a plate having a thickness of 1.0 mm using an extrusion molding machine. Thus, a base material layer was prepared. Next, a urethane acrylate resin (4% by mass of Merck Darocur 1173 is blended with 100% by mass of UV7605B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a UV curable resin material is coated on the base layer at a thickness of 1 μm. did. Next, the test body of Example 1 was obtained by irradiating with ultraviolet rays and performing a curing treatment. In addition, the cross-sectional enlarged electron micrograph of the PMMA resin composition (Arkema Co., Ltd. make, OLOGLAS HT121) containing the hard dispersion phase used by each Example and a comparative example is attached to FIG. 2 as reference data. The horizontal stripe portion in the drawing indicates the hard dispersed phase, and the other portions indicate the matrix phase (PMMA).

(Example 2)
Molding a resin composition (OROGLAS HT121, manufactured by Arkema Co., Ltd.) containing poly (methyl methacrylate) (PMMA) as a thermoplastic matrix resin material into a plate having a thickness of 1.0 mm using an extrusion molding machine. Thus, a base material layer was prepared. Next, on the base material layer, a urethane acrylate resin (UV7605B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., 100% by mass and 4% by mass of Darocur 1173 manufactured by Merck) is coated at a thickness of 5 μm as an ultraviolet curable resin material. did. Next, the test body of Example 2 was obtained by irradiating with ultraviolet rays and performing a curing treatment.

(Comparative Example 1)
Forming a resin composition (ORKELA HT121, manufactured by Arkema Co., Ltd.) containing poly (methyl methacrylate) (PMMA) as a thermoplastic matrix resin material into a plate having a thickness of 1.0 mm using an extrusion molding machine. Thus, a test body of Comparative Example 1 was obtained.

(Comparative Example 2)
The specimen of Comparative Example 2 was formed by molding polymethyl methacrylate (PMMA) (manufactured by Mitsubishi Rayon Co., Ltd., Acrypet V001) as a thermoplastic matrix resin material into a plate shape having a thickness of 1.0 mm using an extrusion molding machine. Got.

(Comparative Example 3)
A base material layer was prepared by molding polymethyl methacrylate (PMMA) (manufactured by Mitsubishi Rayon Co., Ltd., Acripet V001) as a thermoplastic matrix resin material into a plate shape having a thickness of 1.0 mm using an extrusion molding machine. Next, a urethane acrylate resin (4% by mass of Merck Darocur 1173 is blended with 100% by mass of UV7605B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a UV curable resin material is coated on the base layer at a thickness of 5 μm did. Next, the test body of the comparative example 3 was obtained by irradiating an ultraviolet-ray and performing a hardening process.

(Pencil hardness)
As an index of scratch resistance, the pencil hardness evaluation described in JIS K 5600 was performed. A 1 kg weight was placed on the weight table, extruded at a uniform speed, and a width of about 1 cm was scratched on the surface. Each time it was scratched, the tip of the pencil lead was newly sharpened, and the test was repeated 5 times with a pencil having the same density symbol. The test pencil was 2H-6H specified in JIS S6006. The highest pencil hardness with which the scratches were 3 times or less in 5 tests was described.

(Abrasion resistance (abrasion resistance) test)
A # 0000 steel wool was attached to the tip of an abrasion tester (Honko Seisakusho), and the surface when subjected to 10 reciprocating frictions with a load of 1000 g was visually evaluated according to the following criteria. ○: Evaluation was made in two stages: scars were scarce, and scratches were scratched.

(Evaluation results)
The evaluation results of each example are shown in Table 1.

From the results shown in Table 1, it was shown that in Examples 1 and 2, when a hard coat layer having a thickness of 1 or 5 μm was provided, scratch resistance was obtained as compared with Comparative Examples 1 and 2. Further, in Comparative Example 3, it was shown that even when the hard coat layer was 5 μm, the scratch resistance was lowered when the hard dispersed phase was not present in the base material layer. In Comparative Example 3, it is necessary to further increase the thickness of the hard coat layer in order to obtain scratch resistance equal to or higher than that in each Example. In such a case, there is a risk that warping, undulation, peeling, etc. may occur as the hard coat layer hardens or shrinks. Therefore, in a base material layer containing a hard dispersed phase and composed of an acrylic resin, by laminating a hard coat layer having a thickness of 1 to 5 μm, the hard coat layer is not scratched without causing a warp or the like. It can be seen that the property can be improved.

In addition, you may change the said embodiment as follows.
-The application of the scratch-resistant resin laminate 11 of the above embodiment is not particularly limited. For example, it can be used for synthetic resin moldings such as various displays, various films, decorative sheets, and various electronic components.

-The thickness of the base material layer 12 of the said embodiment is not specifically limited. Further, the shape may be not only a layer shape but also a thin film shape, a sheet shape, a thick molded body, and the like.
In the above embodiment, the substrate 14 is an acrylic resin that does not include a hard dispersed phase. However, the material components that can be used in the substrate 14 are not particularly limited, and can be appropriately selected according to the purpose of use. For example, it may be a film, a sheet, or other metal plate made of a thermosetting resin, a thermoplastic resin, an elastomer, rubber, or the like.

  -In the said embodiment, in the range which does not impair the effect of this invention in the base material layer 12, the hard-coat layer 13, and the board | substrate 14, a polymerization initiator, antioxidant, a light stabilizer, a plasticizer, sensitization as an additive You may mix | blend an agent etc.

In the above embodiment, the hard coat layer 13 is a single layer. However, as long as it is within the range of a predetermined thickness, the structure of the multilayer body of two or more layers may be sufficient.
In the above embodiment, the hard coat layer 13 is laminated as the scratch-resistant resin layer. However, a resin material such as a thermosetting resin having scratch resistance other than the resin material constituting the hard coat layer 13 described above may be used. Examples of the thermosetting resin include phenol resin and melamine resin.

  In the above embodiment, the hard dispersed phase is composed of a thermosetting resin. However, it is not limited to them, and fibers such as UV curable resin, electron beam curable resin, rayon, nylon, aramid, carbon fiber, glass fiber, etc., which have better heat resistance or scratch resistance than thermoplastic matrix resin. Inorganic fillers (reinforcing agents) such as a filler, talc, mica, silica, ferrite, and carbon black may be used.

Next, technical ideas that can be grasped from the above-described embodiment and other examples will be described below together with their effects.
(A) Process of forming a base material by molding an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase, and a thickness of 1 to 5 μm by laminating an abrasion-resistant resin on the base material A method for producing a scratch-resistant resin laminate comprising the step of preparing a scratch-resistant resin layer. According to the configuration of (a), the scratch-resistant resin laminate is obtained by the synergistic effect of the hard dispersed phase contained in the acrylic resin constituting the substrate and the scratch-resistant resin layer laminated on the substrate. It is possible to improve the scratch resistance.

The scratch-resistant resin laminate of this embodiment. (A) A scratch-resistant resin laminate having hard coat layers on both sides of the base material layer. (B) A scratch-resistant resin laminate having a hard coat layer only on the surface (upper surface) of the base material layer. (C) A scratch-resistant resin laminate in which a base material layer and a hard coat layer are laminated on the front surface and the back surface of a substrate, respectively. The cross-sectional enlarged electron micrograph of the PMMA resin composition (Arkema Co., Ltd. product, OLOGLAS HT121) containing the hard dispersion phase used by each Example and a comparative example.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Scratch-resistant resin laminated body, 12 ... Base material layer, 13 ... Hard-coat layer, 14 ... Substrate

Claims (4)

  A scratch-resistant resin laminate in which a scratch-resistant resin layer having a thickness of 1 to 5 μm is laminated on a base material composed of an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase.   The scratch-resistant resin laminate according to claim 1, wherein the acrylic resin is polymethyl methacrylate.   The scratch-resistant resin laminate according to claim 1 or 2, wherein the scratch-resistant resin layer is a hard coat layer.   A base material layer composed of an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase is laminated on the surface of the substrate composed of an acrylic resin, and further, a thickness of 1 to 5 μm is formed on the base material layer. A scratch-resistant resin laminate in which the scratch-resistant resin layer is laminated.