JP7121201B2 - Polycarbonate resin laminate with hard coat layer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polycarbonate resin laminate with a hard coat layer.

Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, etc., and are therefore widely used in electrical, mechanical, automotive, medical applications, and the like. On the other hand, in recent years, polycarbonate resins have been widely used for various transparent members due to the various excellent features described above. In particular, attempts have been widely made to apply it to transparent members for vehicles (hereinafter also referred to as "vehicle glazing members") for the purpose of weight reduction. Vehicle glazing members include headlamp lenses, resin window glass, rear lamp lenses, and meter covers. These members are characterized by complicated shapes and large sizes, and extremely high requirements for the quality of molded products.

As described above, in vehicle glazing members, in addition to good transparency, weather resistance and molding heat resistance, it has good mold releasability, reduced internal distortion of molded products, and improved crack resistance. There is a need for polycarbonate resin compositions.

For example, in Japanese Patent No. 4046159, 100 parts by weight of a polycarbonate resin (component A), 0.005 to 2 parts by weight of a full ester of pentaerythritol and an aliphatic carboxylic acid (component B), and an ultraviolet absorber (component C ) 0.005 to 3 parts by weight of a resin composition, wherein (i) the aliphatic carboxylic acid of the B component contains a palmitic acid component and a stearic acid component, and the gas chromatograph-mass spectrometry (GC / MS method), the sum of the area of the palmitic acid component (Sp) and the area of the stearic acid component (Ss) is 80% or more in the total aliphatic carboxylic acid component, and the area ratio (Ss/ Sp) is from 1.3 to 30, and (ii) the component B has a viscosity average molecular weight of 24,500. A polycarbonate resin composition is disclosed which is characterized by a critical stress of 12 MPa or more when treated at a temperature of 120° C. for 24 hours.

Furthermore, vehicle glazing members are often subjected to surface treatment such as hard coating treatment, but the surface treatment may cause cracks in the molded product. It is thought that this promotes the occurrence of cracks in the product, and improvement is required.
Vehicle glazing members are required to have weather resistance because they may be exposed to harsh environments.
According to one embodiment of the present invention, a polycarbonate resin laminate with a hard coat layer having excellent weather resistance is provided.

The present invention includes the following aspects.
<1> A permeation layer (B layer) and a hard coat layer (C layer) are laminated in this order on at least one surface of a polycarbonate resin substrate layer (A layer) having a thickness of 1 mm to 20 mm, and The A layer, the B layer, and the C layer satisfy the following requirements (a) to (e),
The B layer is in contact with the A layer and the C layer,
A polycarbonate resin laminate with a hard coat layer.
(a) The polycarbonate resin substrate layer contains a polycarbonate resin having a viscosity average molecular weight of 17,000 to 40,000.
(b) The B layer contains both the A layer and the C layer.
(c) The total thickness of the B layer and the C layer is 16 μm to 32 μm.
(d) The thickness of the layer B is 6 μm to 9 μm.
(e) The C layer satisfies the following (A) to (I).
(A) A composition containing inorganic fine particles in which the layer C contains a composite resin C1, a (meth)acrylate compound C2, silica fine particles C3, a triazine-based ultraviolet absorber C4, and a non-reactive silicone surface conditioner C5. A hard coat layer that is a cured product of
The composite resin C1 has a structural unit represented by the following formula (1) and / or the following formula (2), a polysiloxane segment (C1-1) having a silanol group and / or a hydrolyzable silyl group, A composite resin in which a vinyl polymer segment (C1-2) is bonded by a bond represented by the following formula (3).

In the above formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH=CH ₂ , -R ⁴ -C(CH ₃ )=CH ₂ , -R ⁴ A group having at least one polymerizable double bond selected from the group consisting of —O—CO—C(CH ₃ )=CH ₂ and —R ⁴ —O—CO—CH=CH ₂ (provided that R ⁴ represents a single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or 7 to 12 aralkyl groups, and at least one of R ¹ , R ² and R ³ represents the group having the polymerizable double bond.

In general formula (3), a carbon atom represents a partial structure of (C1-2), and Si ^* represents a partial structure of (C1-1).

(B) The compounding ratio of the composite resin C1 is 5% by mass to 15% by mass with respect to the total amount of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3.
(C) the content of the polysiloxane segment (C1-1) in the composite resin C1 is 55% by mass to 65% by mass with respect to the total solid content of the composite resin C1;
(D) the (meth)acrylate compound C2 is an isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) represented by the following general formula (4);
an isocyanuric ring-containing tri(meth)acrylate compound (C2-2) represented by the following general formula (5);
and an aliphatic di(meth)acrylate compound (C2-3).

In general formula (4), R ⁵ , R ⁶ and R ⁷ each independently represent a group represented by formula (4-a) or formula (4-b) below.

In the above formula (4-a), n1 represents an integer of 2 to 4, R ⁸ represents a hydrogen atom or a methyl group, Q ¹ and Q ² each independently represent a hydrogen atom or a represents an alkyl group, and at least one of Q ¹ and Q ² represents an alkyl group.

In general formula (5) above, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a group represented by formula (5-a) below.

In the above formula (5-a), n2 represents an integer of 2 to 4, R ⁸ represents a hydrogen atom or a methyl group, Q ³ and Q ⁴ are each independently a hydrogen atom or a represents an alkyl group.

(E) The blending ratio of the (meth)acrylate compound C2 is 70% by mass to 90% by mass with respect to the total amount of the composite resin C1, the (meth)acrylate compound C2 and the silica fine particles C3.
(F) the isocyanurate ring-containing urethane (meth)acrylate compound (C2-1), the isocyanurate ring-containing tri(meth)acrylate compound (C2-2) and the aliphatic di(meth)acrylate compound (C2-3) With respect to the total amount, the blending ratio of the isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) is 21% by mass to 33.5% by mass, and the isocyanuric ring-containing tri(meth)acrylate compound (C2- 2) is 60% to 70% by mass, and the aliphatic di(meth)acrylate compound (C2-3) is 6.5% to 9% by mass.
(G) The blending ratio of the silica fine particles C3 is 5% by mass to 15% by mass with respect to the total amount of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3.
(H) The content of the triazine-based ultraviolet absorber C4 is 3% by mass to 5% by mass with respect to a total of 100 parts by mass of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3.
(I) The blending amount of the non-reactive silicone surface conditioner C5 is 0.05% by mass to 1% by mass with respect to a total of 100 parts by mass of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3. %.
<2> The polycarbonate resin laminate with a hard coat layer according to <1>, wherein the ratio of the thickness of the B layer to the total thickness of the B layer and the C layer is 20% to 50%. body.
<3> The polycarbonate resin laminate with a hard coat layer according to <1> or <2>, wherein the polycarbonate resin is an aromatic polycarbonate resin.
<4> The aliphatic di(meth)acrylate compound (C2-3) is 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, or 1,10-decanediol The polycarbonate resin laminate with a hard coat layer according to any one of <1> to <3>, which is a di(meth)acrylate.
<5> When the cross section of the layer B is analyzed using a microscopic FT-IR measurement device, a peak derived from a carbonate bond and a peak derived from an acrylic ester are mixed, <1> to <4> The polycarbonate resin laminate with a hard coat layer according to any one of .

According to one embodiment of the present invention, it is possible to provide a polycarbonate resin laminate with a hard coat layer having excellent weather resistance.

FIG. 1 shows a schematic front view of an injection-molded article formed of an aromatic polycarbonate produced in an example. FIG. 2 shows a scanning electron microscope (SEM) photograph of a cross-section of a laminate according to the present disclosure.

The content of the present disclosure will be described in detail below. Although the description of the constituent elements described below may be made based on representative embodiments of the present disclosure, the present disclosure is not limited to such embodiments.
In this specification, the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.
In addition, in the description of groups (atomic groups) in the present specification, the descriptions that do not indicate substitution or unsubstituted include those having no substituents as well as those having substituents. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
In the present specification, "(meth)acrylic" is a term used as a concept that includes both acrylic and methacrylic, and "(meth)acryloyl" is a term that is used as a concept that includes both acryloyl and methacryloyl. is.
In addition, the term "step" in this specification is not limited to independent steps, and even if it cannot be clearly distinguished from other steps, if the intended purpose of the step is achieved included.
Further, in the present disclosure, "% by mass" and "% by weight" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.
Unless otherwise specified, in the present disclosure, each component in the composition or each structural unit in the polymer may be contained singly or in combination of two or more. .
Furthermore, in the present disclosure, when there are multiple substances or structural units corresponding to each structural unit in the polymer, the amount of each structural unit in the polymer is the amount of each of the corresponding multiple structural units present in the polymer unless otherwise specified. Means the total amount of units.
Furthermore, in the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.

(Polycarbonate resin laminate with hard coat layer)
A polycarbonate resin laminate with a hard coat layer (hereinafter also simply referred to as "laminate") according to an embodiment of the present disclosure includes at least one polycarbonate resin substrate layer (A layer) having a thickness of 1 mm to 20 mm. A permeation layer (B layer) and a hard coat layer (C layer) are laminated in this order on the surface, and satisfy the following requirements (a) to (e), and the B layer is the A layer and the C layer. bordering on
(a) The polycarbonate resin contained in the polycarbonate resin substrate layer has a viscosity average molecular weight of 17,000 to 40,000.
(b) The B layer contains both the A layer and the C layer.
(c) The total thickness of the B layer and the C layer is 16 μm to 32 μm.
(d) The thickness of the layer B is 6 μm to 9 μm.
(e) The C layer satisfies the following (A) to (I).

As a result of intensive studies by the present inventors, it was found that a molded article formed from the polycarbonate resin composition described in Japanese Patent No. 4046159 requires further improvement in weather resistance.
Normally, a thermoplastic resin such as an aromatic polycarbonate resin and a thermosetting resin used in a hard coat layer have different thermal shrinkage rates, so it has been difficult to laminate a thermosetting resin on a thermoplastic resin. . Therefore, as a result of intensive studies by the present inventors, a permeation layer (B layer) and a hard material satisfying (A) to (I) are added to at least one surface of a polycarbonate resin base material layer (A layer) having a specific thickness. The coat layer (C layer) is laminated in this order, satisfies the requirements of (a) to (e) above, and the B layer is in contact with the A layer and the C layer, and has excellent weather resistance. It was found that a polycarbonate resin base material with a hard coat layer can be obtained.
Although the detailed mechanism by which the above effect is obtained is unknown, it is presumed as follows.

In the hard coat layer (layer C), an inorganic fine particle dispersion containing a composite resin C1, a (meth)acrylate compound C2, silica fine particles C3, a triazine-based ultraviolet absorber C4, and a non-reactive silicone surface conditioner C5 is used. Among these components, the solubility parameters of the acrylate compound C2 and the composite resin C1 are particularly close to those of the polycarbonate, and the affinity between the two is high, increasing the intermolecular force at the interface. In addition, in the hard coat layer-attached polycarbonate resin laminate according to the present disclosure, the B layer includes both the A layer and the C layer. Therefore, it is presumed that the adhesion between the C layer and the A layer is further improved by interposing the B layer.
In addition, the composite resin C1 having a polysiloxane segment having a silanol group and/or a hydrolyzable silyl group and a vinyl-based polymer segment contained in the inorganic fine particle dispersion can easily form inorganic fine particles such as silica fine particles C3. can be dispersed. Furthermore, since the composite resin C1 has a polymerizable double bond, it can be cured with active energy rays such as ultraviolet rays. Since the (meth)acrylate compound C2 has a polymerizable double bond that can be copolymerized with the composite resin C1, the composite resin C1 and the (meth)acrylate compound C2 are three-dimensionally crosslinked. Therefore, it is presumed that the resulting hard coat layer (coating film) has excellent surface physical properties and weather resistance, as well as abrasion resistance and boiling water resistance. In particular, since the resin used for the hard coat layer (C) is an acrylic resin with a three-dimensional crosslinked structure that acts as a binding point due to the intermolecular force of the inorganic fine particles, both the elastic deformation region and the nondestructive plastic deformation region are widened. It is presumed to be excellent in weather resistance under more severe conditions (du-cycle super-accelerated weather resistance).
In addition, in the laminate according to the present disclosure, the A layer, the B layer, and the C layer satisfy the above requirements (a) to (e), so that the haze value can be kept low and the total light transmittance is also excellent. .

In the laminate according to the present disclosure, a permeation layer (B layer) and a hard coat layer (C layer) are laminated on both sides of a polycarbonate resin base layer (A layer), and the B layer is the A layer and the C layer. in contact with
Further, in the laminate according to the present disclosure, other layers may be laminated on the hard coat layer (C layer), if necessary.
Other layers include, for example, a decorative layer.
A known decorating method can be used as a method for forming the decorating layer. For example, a decorating sheet is formed into a three-dimensional shape in advance using a vacuum molding die, the formed sheet is inserted into an injection mold, Insert molding method in which resin (laminate) in a fluid state is injected into the mold to integrate the resin and molded sheet. There is known a simultaneous injection-molding decoration method in which the surface of an injection-molded article is decorated by integrating it with a melted resin.

<< Layer A >>
The polycarbonate resin used in the polycarbonate resin layer of the laminate according to the present disclosure is preferably an aromatic polycarbonate resin, more preferably an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor. preferable.
Examples of the reaction method include interfacial polycondensation, melt transesterification, solid-phase transesterification of a carbonate prepolymer, and ring-opening polymerization of a cyclic carbonate compound.

Representative examples of dihydric phenols used herein include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy-3,5-dimethyl) phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A ), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis{(4-hydroxy-3,5-dimethyl)phenyl}propane, 2,2-bis{(3 -isopropyl-4-hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4 -hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2-bis( 4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4 -isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis{(4-hydroxy-3 -methyl)phenyl}fluorene, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, α,α'-bis( 4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4, 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenyl ester. These can be used alone or in combination of two or more.

Among the above dihydric phenols, bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4- hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis( 4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene. Copolymers or copolymers are preferred, in particular homopolymers of bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane with bisphenol A, 2,2-bis{(4- A copolymer with hydroxy-3-methyl)phenyl}propane or α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene is more preferably used.
Carbonate precursors include, for example, carbonyl halides, carbonate esters, and haloformates, specifically phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

A method for synthesizing a polycarbonate resin by the interfacial polycondensation method and the transesterification method will be briefly described below.
In the interfacial polycondensation method using phosgene as a carbonate precursor, the reaction between the dihydric phenol component and phosgene is usually carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amine compounds such as pyridine are used. Examples of organic solvents include halogenated hydrocarbons such as methylene chloride and chlorobenzene. In order to accelerate the reaction, for example, catalysts such as tertiary amines and quaternary ammonium salts can be used. It is desirable to use a terminating agent.
The reaction temperature is generally 0° C. to 40° C., the reaction time is 10 minutes to 5 hours, and the pH is preferably maintained at 10 or higher during the reaction.

In the transesterification method (melting method) using a carbonic acid diester as a carbonate precursor, a predetermined proportion of a dihydric phenol component and a carbonic acid diester are heated and stirred in the presence of an inert gas, and the resulting alcohol or phenol is distilled off. It's a way to get it out.
Although the reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, it is usually preferably in the range of 120°C to 350°C. As for the reaction method, it is preferable to carry out the reaction while reducing the pressure from the initial stage of the reaction and distilling off the alcohol or phenol produced.
In addition, a conventional transesterification reaction catalyst can be used to promote the reaction. Carbonic acid diesters used in this transesterification reaction include, for example, diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate, with diphenyl carbonate being particularly preferred.

(a) The polycarbonate contained in the polycarbonate resin substrate layer (layer A) has a viscosity average molecular weight of 17,000 to 40,000, preferably 20,000 to 30,000. Moreover, the polycarbonate is preferably produced by an interfacial polycondensation method or a transesterification method.
When the viscosity-average molecular weight of the polycarbonate resin is 17,000 to 40,000, the obtained laminate has sufficient strength and good melt fluidity, and thus has excellent weather resistance, boiling resistance and abrasion resistance. Above all, it is superior in weather resistance.
The viscosity-average molecular weight (M) referred to here is obtained from the following Schnell viscosity formula by determining the intrinsic viscosity [η] of a solution measured at 20° C. using methylene chloride as a solvent using an Ostwald viscometer.
[η]=1.23×10 ⁻⁴ M ^0.83

The polycarbonate resin substrate layer (layer A) may contain a polycarbonate resin having a viscosity average molecular weight other than 17,000 to 40,000 and a resin other than the polycarbonate resin, but preferably does not contain these.
In the polycarbonate resin base material layer (A layer), from the viewpoint of abrasion resistance, boiling water resistance and weather resistance, the content of polycarbonate resins other than the viscosity average molecular weight of 17,000 to 40,000 is the total weight of the A layer is preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.

In addition, according to the purpose of use, the polycarbonate resin may be added with conventional additives such as heat stabilizers, release agents, infrared absorbers, ultraviolet absorbers, as long as the light transmittance is not impaired. Antioxidants, light stabilizers, foaming agents, reinforcing agents (e.g., talc, mica, clay, wollastonite, calcium carbonate, glass fibers, glass beads, glass balloons, milled fibers, glass flakes, carbon fibers, carbon flakes, Carbon beads, carbon milled fibers, metal flakes, metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductivity carbon black and various whiskers), flame retardants (e.g., halogen-based flame retardants, phosphate ester-based flame retardants, metal salt-based flame retardants, red phosphorus-based flame retardants, silicon-based flame retardants, fluorine-based flame retardants, and metal water flame retardants), coloring agents (e.g., carbon black, pigments such as titanium oxide, and dyes), light diffusing agents (e.g., acrylic crosslinked particles, silicon crosslinked particles, ultra-thin glass flakes, and calcium carbonate particles), Fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., microparticle titanium oxide and microparticle zinc oxide), grafting An impact modifier typified by rubber or a photochromic agent can be blended.

Any method is employed to produce the polycarbonate resin. As a method for producing a polycarbonate resin, for example, polycarbonate resin raw materials and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, and then granulation with an extrusion granulator or a briquetting machine, followed by melt kneading with a melt kneader typified by a vented twin-screw extruder, and pelletization with a device such as a pelletizer.

In addition, as a method for producing a polycarbonate resin, a method of supplying each component independently to a melt kneader typified by a vented twin-screw extruder, and after premixing a part of each component, the remaining A method of supplying the components to the melt-kneader independently of each other is also possible. As a method of pre-mixing a part of each component, for example, after pre-mixing additives such as phosphorus stabilizers and hindered phenol-based antioxidants, the mixture is mixed with the polycarbonate resin or directly supplied to an extruder. is mentioned.

Further, as a method of premixing, for example, in the case of including those in the form of powder, a method of blending a part of such powder and additives to be blended to make a masterbatch of additives diluted with powder can be mentioned. be done. Furthermore, as a method of premixing, a method of supplying one component independently from the middle of a melt extruder may be used. When the components to be blended include liquid ones, a so-called liquid injection device or liquid addition device can be used for feeding to the melt extruder.

As the extruder, an extruder having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to install a screen in front of the die portion of the extruder to remove foreign matter and the like mixed in the extruded raw material to remove the foreign matter from the resin composition.
Such screens can include wire mesh, screen changers, and sintered metal plates (such as disc filters).

Examples of the melt-kneader include a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more screws, in addition to the twin-screw extruder.

The resin extruded as described above is either directly cut into pellets or pelletized by forming strands and then cutting the strands with a pelletizer. It is preferable to clean the atmosphere around the extruder when it is necessary to reduce the influence of external dust during pelletization.

Polycarbonate resins can be used to produce various products by generally injection-molding polycarbonate resin pellets to obtain molded articles.
In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas assist injection molding, insert molding, in-mold coating molding, heat insulation mold molding, rapid heating and cooling mold molding, two-color molding, Sandwich molding and ultra-high speed injection molding can be mentioned.
For molding, either a cold runner method or a hot runner method can be selected.

Polycarbonate resins can also be used in the form of various shaped extruded products, sheets, films, etc. by extrusion molding. In addition, inflation method, calendering method, or casting method can also be used for forming sheets and films. Further, the polycarbonate resin can be molded as a heat-shrinkable tube by subjecting it to a specific stretching operation. Polycarbonate resin can also be made into hollow molded articles by rotational molding or blow molding.

The thickness of the polycarbonate resin substrate layer (A layer) is 1 mm to 20 mm, preferably 2 mm to 20 mm, more preferably 3 mm to 15 mm.
The thickness of the polycarbonate resin substrate layer (A layer) is measured by measuring the thickness of the laminate according to the present disclosure with a micrometer, and from the thickness of this laminate, the B layer and C measured with a scanning electron microscope (SEM). It is calculated by subtracting the layer thickness.
The thicknesses of the layers B and C are obtained by measuring the cross section of the laminate according to the present disclosure with a scanning electron microscope (SEM).

<< B layer >>
(b) The B layer contains both the A layer and C layer components. By including both components of the A layer and the C layer in the B layer, the adhesion of each layer can be improved.
In addition, "including both the components of the A layer and the C layer" means that part or all of the components included in the A layer and part or all of the components included in the C layer are included.

Both components of A layer and C layer contained in B layer are confirmed by microscopic-infrared spectroscopy (microscopic FT-IR method).
Specifically, the laminate according to the present disclosure is cut, the cross section of the B layer is analyzed using a microscopic FT-IR measurement device, and the peak derived from the carbonate bond (1780 cm ^-1 ) and the peak derived from the acrylic ester (near 1740 cm ⁻¹ ) to confirm that both components of the A layer and the C layer are mixed, that is, the B layer contains both the A layer and the C layer components. can be done.

When the cross section of layer B is analyzed using a microscopic FT-IR measuring device, it is preferable that peaks derived from carbonate bonds and peaks derived from acrylic esters coexist.

When analyzed using a microscopic FT-IR measurement device at a position 1 μm in the thickness direction from the A layer side of the B layer, the ratio of the peak derived from the carbonate bond and the peak derived from the acrylic ester was 5: A ratio of 1 to 1:2 is preferred.

From the viewpoint of excellent wear resistance, boiling water resistance, and weather resistance, the B layer preferably contains the component contained in the A layer and the component contained in the C layer. As a component contained in the A layer, the B layer preferably contains a polycarbonate resin. As a component contained in the C layer, the B layer preferably contains a crosslinked product of the composite resin C1 and the (meth)acrylate compound C2. In addition, the layer B may contain the composite resin C1 and may contain the (meth)acrylate compound C2.

(d) The thickness of the B layer is 6 μm to 9 μm. When the thickness of the B layer is 6 μm or more, the boiling water resistance is excellent, and when the thickness is 9 μm or less, the abrasion resistance and weather resistance are excellent. The thickness of the layer B is preferably 6 μm to 8 μm from the viewpoint of the obtained laminate having excellent abrasion resistance, boiling water resistance and weather resistance. The thickness of the B layer can be adjusted by the coating amount of the inorganic fine particle dispersion contained in the C layer. The thickness of the B layer can be obtained by the same method as that for the A layer.

(c) The total thickness of the B layer and the C layer is 16 μm to 32 μm. When the total thickness of the B layer and the C layer is 16 μm or more, the weather resistance is excellent. It never gets too big. In addition, during curing, active energy rays such as ultraviolet rays reach the interface between the B layer and the A layer, and the C2 component in the B layer near the interface with the A layer also undergoes a sufficient addition reaction, so it has excellent boiling water resistance. . From the viewpoint of abrasion resistance, boiling water resistance and weather resistance, the total thickness of the B layer and the C layer is preferably 18 μm to 28 μm, more preferably 18 μm to 25 μm.
The total thickness of the B layer and the C layer can be adjusted by the coating amount of the inorganic fine particle dispersion contained in the C layer. In addition, the total thickness of the thickness of the B layer and the thickness of the C layer can be obtained by the same method as for the thickness of the A layer.

From the viewpoint of abrasion resistance, boiling water resistance, weather resistance, and low initial haze, the ratio of the thickness of the B layer to the total thickness of the B layer and the C layer is 20% to 50%. 20% to 40% is more preferable, 25% to 35% is still more preferable, and 25% to 30% is particularly preferable.

<<C layer>>
(e) The C layer satisfies (A) to (I) below.
The layer C is a cured product of an inorganic fine particle-containing composition containing a composite resin C1, a (meth)acrylate compound C2, silica fine particles C3, a triazine-based ultraviolet absorber C4, and a non-reactive silicone surface conditioner C5. is the hard coat layer. Each component is preferably dispersed in the inorganic fine particle-containing composition. Hereinafter, the inorganic fine particle-containing composition is also referred to as "inorganic fine particle dispersion".
Details of each component contained in the inorganic fine particle dispersion will be described below.

[(A)]
<<Composite resin C1>>
The inorganic fine particle dispersion used in the C layer contains the composite resin C1.
Composite resin C1 comprises a polysiloxane segment (C1-1) having structural units represented by the following formulas (1) and/or formula (2), a silanol group and/or a hydrolyzable silyl group, and a vinyl polymer. Combined segment (C1-2) is a composite resin bonded by a bond represented by the following general formula (3).

In the above formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH=CH ₂ , -R ⁴ -C(CH ₃ )=CH ₂ , -R ⁴ A group having at least one polymerizable double bond selected from the group consisting of —O—CO—C(CH ₃ )=CH ₂ and —R ⁴ —O—CO—CH=CH ₂ (provided that R ⁴ represents a single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or 7 to 12 aralkyl groups, and at least one of R ¹ , R ² and R ³ represents the group having the polymerizable double bond.

In general formula (3), carbon atoms represent a portion of the vinyl polymer segment (C1-2), and Si ^* represents a portion of the polysiloxane segment (C1-1).

In the inorganic fine particle dispersion containing the composite resin C1, at least one of R ¹ , R ² and R ³ in the above formulas (1) and (2) is a group having a polymerizable double bond. Therefore, the injection-molded hard coat layer according to the present disclosure can be cured by the active energy ray, and the crosslink density of the coating film is improved by the active energy ray and the condensation reaction of the silanol group and/or the hydrolyzable silyl group. By these two curing mechanisms, it is possible to form a cured product having superior abrasion resistance, boiling water resistance, and weather resistance. In addition, the inorganic fine particle dispersion containing the composite resin C1 is also used for automobile exterior paints and substrates that are easily deformed by heat, such as plastics, for which it was difficult to use a thermosetting resin composition. It can be used preferably.

-Polysiloxane segment (C1-1)-
The polysiloxane segment (C1-1) has a structural unit represented by formula (1) and/or formula (2) above, and a silanol group and/or a hydrolyzable silyl group.

The alkylene group having 1 to 6 carbon atoms in R ⁴ may be a linear or branched alkylene group. Examples of the alkylene group include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, isopentylene group, neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohesylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group Lene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1,2-trimethylpropylene group, 1,2,2-trimethyl Propylene groups, 1-ethyl-2-methylpropylene groups, and 1-ethyl-1-methylpropylene groups are included.
Among them, R ⁴ is preferably a single bond or an alkylene group having 2 to 4 carbon atoms, more preferably a linear alkylene group having 2 to 4 carbon atoms, because of the availability of raw materials. A linear alkylene group having 2 or 3 carbon atoms is more preferable.

The alkyl group having 1 to 6 carbon atoms in R ¹ , R ² and R ³ may be a linear or branched alkylene group. Alkyl groups include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1 -methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohesyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1 -dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl- 2-methylpropyl group, and 1-ethyl-1-methylpropyl group.
Examples of cycloalkyl groups having 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups.
Examples of the aryl group include phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group, and 3-isopropylphenyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, diphenylmethyl group and naphthylmethyl group.

at least one of R ¹ , R ² and R ³ is -R ⁴ -CH=CH ₂ , -R ⁴ -C(CH ₃ )=CH ₂ , -R ₄ -O-CO-C(CH ₃ )= CH ₂ and a group having a polymerizable double bond selected from the group consisting of -R ⁴ -O-CO-CH=CH ₂ (hereinafter also simply referred to as a group having a polymerizable double bond). However, R ⁴ represents a single bond or an alkylene group having 1 to 6 carbon atoms.
The group having a polymerizable double bond is -R ⁴ -C(CH ₃ )=CH ₂ or -R ⁴ -O-CO-C(CH ₃ ) is preferably a group represented by = _CH2 .
When the group having a polymerizable double bond has a (meth)acryloyl group (--O--CO--C(CH ₃ )=CH ₂ ), it is highly reactive during UV curing, and the vinyl polymer segment described later The compatibility with (C1-2) is improved.
The term "group having a polymerizable double bond" as used herein is a general term for groups capable of propagating by free radicals, such as vinyl groups and (meth)acryloyl groups.

From the viewpoint of abrasion resistance, boiling water resistance and weather resistance, the group having a polymerizable double bond is preferably present in the polysiloxane segment (C1-1) at least 2 times, and 3 to 200 times. more preferably 3 to 50.
Specifically, when the content of the group having a polymerizable double bond in the polysiloxane segment (C1-1) is 3% by mass to 35% by mass, desired abrasion resistance can be obtained. .
The content of polymerizable double bonds indicates the ratio (% by mass) of the total mass of groups having polymerizable double bonds in the total mass of the polysiloxane segment.

The structural unit represented by formula (1) and/or formula (2) is a three-dimensional network-like polysiloxane structural unit in which two or three silicon bonds are involved in cross-linking. When the composite resin C1 contains structural units represented by the above formula (1) and/or formula (2), it becomes difficult to form a dense network structure while forming a three-dimensional network structure after curing. is suppressed, and the storage stability is also improved.

-Silanol group and/or hydrolyzable silyl group-
Polysiloxane segment (C1-1) has a silanol group and/or a hydrolyzable silyl group.
A silanol group in the present disclosure refers to a silicon-containing group having a hydroxyl group directly bonded to a silicon atom. Specifically, the silanol group is a silanol group formed by bonding an oxygen atom having a bond to a hydrogen atom in the structural unit represented by formula (1) and/or formula (2). preferable.

In the present disclosure, a hydrolyzable silyl group refers to a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom. Specific examples of hydrolyzable groups include groups represented by the following general formula (S-1).
Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups, phenoxy groups, aryloxy groups, mercapto groups, amino groups, amido groups, aminooxy groups, iminooxy groups, and alkenyloxy groups.

In general formula ( ^S -1), R ^S5 represents a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group; a group selected from the group consisting of a mercapto group, an amino group, an amido group, an aminooxy group, an iminooxy group and an alkenyloxy group (hereinafter also referred to as a "hydrolyzable group"); b is an integer of 0 to 2; represents

Examples of alkyl groups in R ^S5 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and tert-pentyl. group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohesyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1 -ethyl-2-methylpropyl group and 1-ethyl-1-methylpropyl group.
Examples of aryl groups include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, and 3-isopropylphenyl groups.
Aralkyl groups include, for example, a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

In R ^{5 S6} , halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
Alkoxy groups include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, and ter-butoxy groups.
Acyloxy groups include, for example, formyloxy, acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, pentanoyloxy, phenylacetoxy, acetoacetoxy, benzoyloxy, and naphthoyloxy.
Aryloxy groups include, for example, phenyloxy and naphthyloxy.
Examples of alkenyloxy groups include vinyloxy, allyloxy, 1-propenyloxy, isopropenyloxy, 2-butenyloxy, 3-butenyloxy, 2-petenyloxy, 3-methyl-3-butenyloxy, and A 2-hexenyloxy group can be mentioned.

By hydrolyzing the hydrolyzable group represented by R ^S6 , the hydrolyzable silyl group represented by general formula (S-1) becomes a silanol group. The hydrolyzable group represented by R ^S6 is preferably a methoxy group and an ethoxy group because of their excellent hydrolyzability.
Further, the hydrolyzable silyl group is, specifically, an oxygen atom having a bond in the structural unit represented by formula (1) and/or formula (2) is bonded to or substituted with the hydrolyzable group. preferably a hydrolyzable silyl group.

A silanol group and/or a hydrolyzable silyl group undergoes a hydrolytic condensation reaction between a hydroxyl group in the silanol group and a hydrolyzable group in the hydrolyzable silyl group. The crosslink density of the siloxane structure is increased, and a hard coat layer having excellent wear resistance and weather resistance can be formed.
Further, the silanol group and/or hydrolyzable silyl group comprises a polysiloxane segment (C1-1) containing a silanol group and/or a hydrolyzable silyl group and a vinyl polymer segment (C1-2) described later, It is used when binding via the bond represented by the general formula (3).

-Vinyl polymer segment (C1-2)-
The vinyl polymer segment (C1-2) contained in composite resin C1 is a vinyl polymer segment such as acrylic polymer or vinyl ester polymer. It is preferable to appropriately select the type of the vinyl polymer segment depending on the application.

The acrylic polymerizable segment (C1-2) is obtained by polymerizing or copolymerizing a general-purpose (meth)acrylic monomer. The (meth)acrylic monomer used for synthesizing the acrylic polymerizable segment (C1-2) is not particularly limited. The acrylic polymerizable segment (C1-2) may also be obtained by copolymerizing a (meth)acrylic monomer and a vinyl monomer.
(Meth)acrylic monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth) Alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms such as acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate; benzyl (meth)acrylate, 2-phenylethyl (meth)acrylate aralkyl (meth)acrylates such as; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; ω such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate -alkoxyalkyl (meth)acrylates; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate and vinyl benzoate; alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; dimethyl malate , di-n-butyl maleate, dimethyl fumarate, dialkyl esters of unsaturated dibasic acids such as dimethyl itaconate; α-olefins such as ethylene and propylene; vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotri fluoroolefins such as fluoroethylene; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; and N,N-dimethyl (meth)acrylamide, N-(meth) Tertiary amide group-containing monomers such as acryloylmorpholine, N-(meth)acryloylpyrrolidine, and N-vinylpyrrolidone are included.

The polymerization method, solvent, and polymerization initiator for copolymerizing the above monomers are not particularly limited, and the vinyl polymer segment (C1-2) can be obtained by a known method.
For example, 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4- dimethylvaleronitrile), 2,2′-azobis(2-methylbutyronitrile), tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di- A vinyl polymer segment (C1-2) can be obtained using a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate and the like.

The number average molecular weight of the vinyl polymer segment (C1-2) is preferably in the range of 500 to 200,000 in terms of number average molecular weight (hereinafter abbreviated as "Mn"). When the number average molecular weight of the vinyl polymer segment (C1-2) is within the above range, it is possible to prevent thickening and gelation during the production of the composite resin C1, and the durability is excellent. From the above viewpoint, Mn is more preferably in the range of 700 to 100,000. A range of 1,000 to 50,000 is more preferable because a good cured film can be formed when forming a layer on a substrate.

Specific examples of the group in which at least one of R ¹ , R ² and R ³ has a polymerizable double bond for the polysiloxane segment (C1-1) include, but are not limited to, the following structures. no. In the structures below, R ¹ , R ² and R ³ represent R ¹ , R ² and R ³ in formulas (1) and (2).

[(F)]
The number of polysiloxane segments (C1-1) contained in composite resin C1 may be one, or two or more.
The content of the polysiloxane segment (C1-1) in the composite resin C1 is 55% by mass to 65% by mass with respect to the total solid content of the composite resin C1. When the content of the polysiloxane segment (C1-1) is within the above range, the abrasion resistance, boiling water resistance and weather resistance are excellent. From the same point of view, the content of the polysiloxane segment (C1-1) is preferably 58% by mass to 63% by mass with respect to the total solid content of the composite resin C1.

[(E)]
The blending ratio of C1 is 5% by mass to 15% by mass with respect to the total amount of composite resin C1, (meth)acrylate compound C2 and silica fine particles C3. When the blending ratio of C1 is within the above range, the abrasion resistance, boiling water resistance and weather resistance are excellent. From the same point of view, the compounding ratio of the composite resin C1 is preferably 5% by mass to 10% by mass with respect to the total amount of the composite resin C1, the (meth)acrylate compound C2 and the silica fine particles C3.

<<(meth)acrylate compound C2>>
The inorganic fine particle dispersion used for the hard coat layer according to the present disclosure contains (meth)acrylate compound C2. (Meth)acrylate compound C2 includes an isocyanurate ring-containing urethane (meth)acrylate compound (C2-1), an isocyanurate ring-containing tri(meth)acrylate compound (C2-2), and an aliphatic di(meth)acrylate compound (C2 -3).

[(H)]
The blending ratio of the (meth)acrylate compound C2 is 70% by mass to 90% by mass, preferably 72% by mass to 88% by mass, with respect to the total amount of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3. % by mass, more preferably 80% by mass to 88% by mass. When the blending ratio of the (meth)acrylate compound C2 is within the above range, the abrasion resistance, boiling water resistance and weather resistance are excellent.

[(G)]
-Isocyanuric ring-containing urethane (meth)acrylate compound (C2-1)-
The isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) is represented by the following general formula (4) and has a structure having an isocyanuric ring structure, a urethane bond and a (meth)acryloyl group.

In formula (4) above, R ⁵ , R ⁶ and R ⁷ each independently represent a group represented by formula (4-a) or formula (4-b) below.

In formula (4-a) above, n1 represents an integer of 2 to 4, R ⁸ represents a hydrogen atom or a methyl group, and Q ¹ and Q ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. group, provided that at least one of Q ¹ and Q ² represents an alkyl group.
The alkyl group having 1 to 5 carbon atoms may be linear or branched, but is preferably linear. The alkyl group having 1 to 5 carbon atoms is preferably a linear alkyl group having 1 to 3 carbon atoms.

The isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) is a compound in which three or more groups having polymerizable unsaturated groups are bonded to the isocyanuric ring structure via urethane bonds.

Compounds forming the group represented by formula (4-a) include hydroxy-alkyl (meth)acrylates, specifically 2-hydroxy-propyl (meth)acrylate, 2-hydroxy-butyl ( meth)acrylates.

Examples of the isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) include a trimer of 1,6-hexanediisocyanate, 2-hydroxy-propyl (meth)acrylate, and 2-hydroxy-butyl (meth)acrylate. , or a compound reacted with pentaerythritol triacrylate.

The blending ratio of the isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) is as follows: 21% by mass to 33.5% by mass with respect to the total amount of the group di(meth)acrylate compound (C2-3). From the viewpoint of abrasion resistance, boiling water resistance and weather resistance, the blending ratio of the isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) is Based on the total amount of the tri (meth) acrylate compound (C2-2) and the aliphatic di (meth) acrylate compound (C2-3) contained, it is preferably 23% by mass to 30% by mass, and 23% by mass to It is more preferably 25% by mass.

<<Isocyanuric ring-containing tri(meth)acrylate compound (C2-2)>>
The isocyanuric ring-containing tri(meth)acrylate compound (C2-2) is represented by the following general formula (5).

In general formula (5) above, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a group represented by formula (5-a) below.

In the above formula (5-a), n2 represents an integer of 2 to 4, R ⁸ represents a hydrogen atom or a methyl group, and Q ³ and Q ⁴ each independently represent a hydrogen atom or 1 carbon atom in the repeating unit. represents an alkyl group of ∼5.

Preferred structures of the isocyanuric ring-containing tri(meth)acrylate compound (C2-2) include the following structures.

The isocyanuric ring-containing tri(meth)acrylate compound (C2-2) may be synthesized or a commercially available product may be used. Commercially available products include M-315 (manufactured by Toagosei Co., Ltd.), A9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-731A (manufactured by Hitachi Chemical Co., Ltd.), SR368 (manufactured by Sartomer), and M -370 (manufactured by MIWON) can be used.

The isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) may be used singly or in combination of two or more.
With respect to the total amount of the isocyanurate ring-containing urethane (meth)acrylate compound (C2-1), the isocyanurate ring-containing tri(meth)acrylate compound (C2-2) and the aliphatic di(meth)acrylate compound (C2-3), The blending ratio of the isocyanuric ring-containing tri(meth)acrylate compound (C2-2) is 60% by mass to 70% by mass, preferably 60% by mass to 69% by mass, and 65% by mass to 69% by mass. is more preferable.

<<Aliphatic di(meth)acrylate compound (C2-3)>>
The aliphatic di(meth)acrylate compound (C2-3) is a compound obtained by esterifying and bonding an alkyldiol and acrylic acid or methacrylic acid.
Aliphatic di(meth)acrylate compounds (C2-3) include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate. ) acrylates are preferred.
The aliphatic di(meth)acrylate compound (C2-3) may be synthesized or a commercially available product may be used. Commercially available products include HDDA (manufactured by Daicel Allnex), A-HD-N, A-NOD-N, A-DOD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,9-DA. (manufactured by Kyoei Chemical Industry Co., Ltd.) can be used.

The aliphatic di(meth)acrylate compounds (C2-3) may be used singly or in combination of two or more.
With respect to the total amount of the isocyanurate ring-containing urethane (meth)acrylate compound (C2-1), the isocyanurate ring-containing tri(meth)acrylate compound (C2-2) and the aliphatic di(meth)acrylate compound (C2-3), The content of the aliphatic di(meth)acrylate compound (C2-3) is 6.5% by mass to 9% by mass, preferably 6.6% by mass to 8.8% by mass, more preferably 6.5% by mass to 9% by mass. It is 6% by mass to 7.5% by mass.

[(I)]
With respect to the total amount of the isocyanurate ring-containing urethane (meth)acrylate compound (C2-1), the isocyanurate ring-containing tri(meth)acrylate compound (C2-2) and the aliphatic di(meth)acrylate compound (C2-3), The blending ratio of the isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) is 21% by mass to 33.5% by mass, and the blending ratio of the isocyanuric ring-containing tri(meth)acrylate compound (C2-2) is 60% by mass. % to 70% by mass, and the blending ratio of the aliphatic di(meth)acrylate compound (C2-3) is 6.5% to 9% by mass.
In the (meth)acrylate compound C2, an isocyanuric ring-containing urethane (meth)acrylate compound (C2-1), an isocyanuric ring-containing tri(meth)acrylate compound (C2-2) and an aliphatic di(meth)acrylate compound (C2-3 ) When the blending amount is within the above range, the abrasion resistance, boiling water resistance and weather resistance are excellent. From the above viewpoint, the total amount of the isocyanurate ring-containing urethane (meth)acrylate compound (C2-1), the isocyanurate ring-containing tri(meth)acrylate compound (C2-2) and the aliphatic di(meth)acrylate compound (C2-3) , the compounding ratio of the isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) is preferably 23% by mass to 30% by mass (more preferably 23% by mass to 25% by mass), and the isocyanuric ring The content of the tri(meth)acrylate compound (C2-2) is preferably 60% by mass to 69% by mass (more preferably 65% by mass to 69% by mass), the aliphatic di(meth)acrylate compound ( The blending ratio of C2-3) is preferably 6.6% by mass to 8.8% by mass (more preferably 6.6% by mass to 7.5% by mass).

<<Silica fine particles C3>>
The inorganic particle dispersion used for the hard coat layer according to the present disclosure contains silica fine particles C3. Silica fine particles C3 are not particularly limited, and known silica fine particles such as colloidal silica can be used.
Commercially available colloidal silica includes, for example, Nissan Chemical Industries, Ltd. methanol silica sol, IPA-ST, PGM-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST- OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, and ST-OL (all product names) can be mentioned.

In addition, as the silica fine particles C3, silica fine particles whose dispersibility is improved by a known method may be used. Such silica fine particles with improved dispersibility include, for example, silica fine particles surface-treated with a reactive silane coupling agent having a hydrophobic group, and those modified with a compound having a (meth)acryloyl group. mentioned. Examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, MIBK-AC, MEK-AC, and PGM-AC (product names) manufactured by Nissan Chemical Industries, Ltd. .

The shape of silica fine particles is not particularly limited, and may be spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous. For example, Silinax manufactured by Nittetsu Mining Co., Ltd. can be used as commercially available hollow silica fine particles.

From the viewpoint of dispersibility in the hard coat layer, the average primary particle size of the silica fine particles C3 is preferably 3 nm to 500 nm, more preferably 5 nm to 300 nm, and even more preferably 10 nm to 100 nm. .
From the viewpoint of dispersibility in the hard coat layer, the silica fine particles C3 are preferably colloidal silica having a spherical shape and an average primary particle size of 5 nm to 100 nm, more preferably 20 nm to 60 nm. is colloidal silica.
The average primary particle size of silica fine particles C3 is measured by observing the hard coat layer in the cross section of the injection molding according to the present disclosure with a transmission electron microscope (TEM).

[(J)]
The silica fine particles C3 may be used singly or in combination of two or more.
The blending ratio of the silica fine particles C3 is 5% by mass to 15% by mass with respect to the total amount of the composite resin C1, the (meth)acrylate compound C2 and the silica fine particles C3. From the viewpoint of , it is preferably 5.5% by mass to 14.5% by mass, more preferably 5.5% by mass to 10% by mass.

<<Triazine-based UV absorber C4>
The inorganic particle dispersion used in the hard coat layer according to the present disclosure contains triazine-based UV absorber C4.
Examples of the triazine-based UV absorber C4 include UV absorbers having a triazine skeleton in the molecular skeleton.
Since the triazine-based ultraviolet absorber C4 has the structure described above, it has excellent ultraviolet absorbing ability. In addition, since the inorganic fine particle dispersion has excellent compatibility with the triazine-based ultraviolet absorber C4, the hard coat layer according to the present disclosure made of the inorganic fine particle dispersion also has excellent light resistance.
Specific examples of the triazine-based ultraviolet absorber C4 include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethyl phenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethylhexyloxy)propyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4- dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine , and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine.
The triazine-based ultraviolet absorber C4 may be synthesized or a commercially available product may be used. As commercially available products, TINUVIN400 (manufactured by BASF), TINUVIN405 (manufactured by BASF), and TINUVIN479 (manufactured by BASF) can be used.

In the triazine-based ultraviolet absorber C4, preferably 2-[4-(octyl-2-methylethanoate)oxy-2-hydroxyphenyl]-4,6-[bis(2,4-dimethylphenyl)]-1, 3,5-triazine, or 2-[4-(2-hydroxy-3-dodecyloxy-propyl)oxy-2-hydroxyphenyl]-4,6-[bis(2,4-dimethylphenyl)-1,3, 5-triazine.

[K]
The triazine-based ultraviolet absorber C4 may be used singly or in combination of two or more.
The amount of the triazine-based ultraviolet absorber C4 is 3% to 5% by mass with respect to a total of 100 parts by mass of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3. From the viewpoint of properties and weather resistance, the content is preferably 3.5% by mass to 4.5% by mass.

<<Non-reactive silicone surface conditioner C5>>
The inorganic particle dispersion used in the hardcoat layer according to the present disclosure contains non-reactive silicone surface modifier C5.
Non-reactive silicone surface modifiers C5 are silicone surface modifiers that do not have reactive groups, specifically polymerizable double bonds. That is, the composite resin C1 is not included in the non-reactive silicone surface conditioner C5. The polymerizable double bond includes the polymerizable double bond in the composite resin C1.
If the silicone surface conditioner contains a reactive group, the resulting hard coat layer becomes rigid and brittle, resulting in poor abrasion resistance and resistance to boiling water.
Examples of the non-reactive silicone surface conditioner C5 include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, and silicone polymers and oligomers having a silicone chain and a polyester chain. Those containing no bond are included.
The non-reactive silicone surface conditioner C5 may be synthesized or a commercially available product may be used. Commercially available products include BYK-300, BYK-302, BYK-320, BYK-325, BYK-326, BYK-330, BYK-333, BYK-342, BYK-375, BYK-377, and BYK-378 ( (manufactured by BYK-Chemie Co., Ltd.).
From the viewpoint of abrasion resistance, boiling water resistance, and weather resistance, the non-reactive silicone surface conditioner C5 is preferably a silicone-based polymer or oligomer having a silicone chain and a polyalkylene oxide chain, or a silicone chain and a polyester chain. It is a silicone-based polymer having BYK-377, BYK-333, or BYK-378 are preferred commercially available non-reactive silicone surface conditioners C5.

[(L)]
The non-reactive silicone surface conditioner C5 may be used singly or in combination of two or more.
The content of the non-reactive silicone surface conditioner C5 is 0.05% by mass to 1% by mass, preferably 0.05% by mass to 1% by mass, based on the total 100 parts by mass of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3. It is more preferably 0.05% by mass to 0.5% by mass.

The inorganic fine particle dispersion contains a composite resin C1, a (meth)acrylate compound C2, silica fine particles C3, a triazine-based ultraviolet absorber C4, and a non-reactive silicone surface conditioner C5. ) With respect to the total amount of the acrylate compound C2 and the silica fine particles C3, the blending ratio of the composite resin C1 is 5% by mass to 15% by mass (preferably 5% by mass to 10% by mass), and the poly The content of the siloxane segment (C1-1) is 55% by mass to 65% by mass (preferably 58% by mass to 63% by mass) relative to the total solid content of the composite resin C1, and the (meth)acrylate compound C2 is 70% by mass to 90% by mass (preferably 72% by mass to 88% by mass, more preferably 80% by mass to 88% by mass), and an isocyanuric ring-containing urethane (meth)acrylate compound (C2 -1) with respect to the total amount of the isocyanuric ring-containing tri(meth)acrylate compound (C2-2) and the aliphatic di(meth)acrylate compound (C2-3), the isocyanuric ring-containing urethane (meth)acrylate compound (C2 -1) is 21% by mass to 33.5% by mass (preferably 23% by mass to 30% by mass, more preferably 23% by mass to 25% by mass), and an isocyanuric ring-containing tri(meth ) The blending ratio of the acrylate compound (C2-2) is 60% by mass to 70% by mass (preferably 60% by mass to 69% by mass, more preferably 65% by mass to 69% by mass), and the aliphatic di (Meth) acrylate compound (C2-3) blending ratio of 6.5% by mass to 9% by mass (preferably 6.6% by mass to 8.8% by mass, more preferably 6.6% by mass to 7% by mass .5% by mass), and the blending ratio of silica fine particles C3 is 5% by mass to 15% by mass (preferably 5.5% by mass to 14.5% by mass, more preferably 5.5% by mass) ~ 10 mass%), and the amount of the triazine-based ultraviolet absorber C4 is 3 mass% to 5 mass% ( (preferably 3.5% by mass to 4.5% by mass), and the amount of the non-reactive silicone surface conditioner C5 to be blended is 100% by mass in total of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3. It is 0.05% by mass to 1% by mass (preferably 0.05% by mass to 0.5% by mass) based on the part.
In the inorganic fine particle dispersion used in the hard coat layer according to the present disclosure, when the blending amounts of C1 to C5 are within the above blending ranges, the hard coat has excellent wear resistance, boiling water resistance, and weather resistance. You can get layers.

-Other ingredients-
The inorganic fine particle dispersion used in the hard coat layer according to the present disclosure may optionally contain components other than the C1 to C5 components (ie, other components). As another component, a dispersion medium may be used for the purpose of adjusting the solid content and viscosity of the dispersion.
The dispersion medium may be any liquid medium that does not impair the effects of the present disclosure, and includes various organic solvents.

From the viewpoint of being able to adjust the layer thickness of the permeation layer (B layer) to a suitable range, organic solvents include alcohols such as methanol, ethanol, propanol, and butanol; dimethyl ether, diethyl ether, methyl ethyl ether, and methyl butyl ether. , tetrahydrofuran, ethers such as dioxane; acetone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), ketones such as cyclohexanone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, propion Esters such as ethyl acetate and ethyl valerate; Alcohols; aliphatic hydrocarbons such as hexane, heptane and octane; and aromatic hydrocarbons such as toluene, xylene, (ethylbenzene), styrene and stilbene.
An organic solvent can be used individually or in mixture.
When an organic solvent is used alone, from the viewpoint of the solubility of the acrylic resin contained in the hard coat layer (C) and the permeability to the polycarbonate resin substrate layer (A layer), the organic solvent may be methoxyethanol, Ether alcohols such as ethoxyethanol, butoxyethanol, methoxypropanol, ethoxypropanol and butoxypropanol are preferred. Among these, in particular, the organic solvent is methoxypropanol from the viewpoint of volatility, dissolving power of acrylic resin, balance of permeability to the polycarbonate resin substrate layer (A layer), and low toxicity. more preferred.
When used in combination with an organic solvent, from the viewpoint of facilitating the formation of the permeation layer (B), the ether alcohols exemplified as the organic solvents when used alone above are further added with acetone, methyl ethyl ketone (2-butanone), methyl ketones such as isobutyl ketone (4-methyl-2-pentanone) and cyclohexanone; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, and ethyl valerate; and toluene, xylene, (ethylbenzene ), styrene, stilbene, and other aromatic hydrocarbons. In addition, since the boiling point is in the range of 70 to 140 ° C., it is possible to delay the volatilization of the solvent and the permeation layer from becoming thicker than necessary when the substrate is thermally dried after the hard coat is applied. It is more preferable to use a mixed solvent in which at least one organic solvent selected from the group consisting of methyl ethyl ketone, ethyl acetate, butyl acetate and toluene is added, and methoxypropanol is mixed with methyl ethyl ketone, ethyl acetate, butyl acetate and toluene. It is particularly preferable to use a mixed solvent containing at least one organic solvent selected from the group consisting of:
In terms of volatility and solvent recovery during coating, the organic solvent is preferably methyl ethyl ketone (MEK) or methoxypropanol (propylene glycol monomethyl ether).

The content of the organic solvent is preferably 40 parts by mass to 70 parts by mass, more preferably 45 parts by mass to 65 parts by mass, based on 100 parts by mass of the inorganic fine particle dispersion.

The inorganic fine particle dispersion used in the hard coat layer according to the present disclosure preferably further contains a photopolymerization initiator when the inorganic fine particle dispersion is cured by ultraviolet rays.
A known photopolymerization initiator may be used, and for example, one or more selected from the group consisting of acetophenones, benzylketals, and benzophenones can be preferably used. The acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone. Examples of the benzyl ketals include 1-hydroxycyclohexyl-phenyl ketone and benzyl dimethyl ketal.
Benzophenones include, for example, benzophenone and methyl o-benzoylbenzoate.
Benzoins include, for example, benzoin, benzoin methyl ether, and benzoin isopropyl ether.

A photoinitiator may be used individually by 1 type, and may use 2 or more types together.
The amount of the photopolymerization initiator used is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 10% by mass, with respect to 100 parts by mass of the composite resin C1.

-Method of forming B layer and C layer-
The method of forming the B layer and the C layer is not particularly limited, and the B layer and the C layer may be formed separately, or the B layer and the C layer may be formed simultaneously. The method for forming the B layer and the C layer includes, for example, coating one surface of the A layer with an inorganic fine particle dispersion to form the B layer, and then coating the B layer with the inorganic fine particle dispersion for forming the C layer. may be applied to form the C layer. Further, the method of forming the B layer and the C layer may be a method of forming the C layer and the B layer by applying an inorganic fine particle dispersion for forming the C layer to one surface of the A layer. .

In the layer B, it is preferable that the difference in solubility parameter between the component C2 of the components forming the layer C and the polycarbonate resin forming the layer A is 10 ((MPa) ^1/2 ) or less. When the difference in solubility parameters is 10 ((MPa) ^1/2 ) or less, both components of the A layer and the C layer are mixed due to diffusion due to molecular motion on the contact surface after coating the A layer with the C layer. A permeation layer (B layer) can be formed.

Examples of the method for forming the B layer and the C layer at the same time include a method in which a coating liquid of the inorganic fine particle dispersion is applied to at least one surface of the polycarbonate resin substrate layer (A layer) and then dried. . The method of simultaneously forming the B layer and the C layer is not limited to this.

The drying method is not particularly limited, and includes natural drying, air drying, and drying by heating.
The drying temperature is preferably 65°C to 95°C, more preferably 70°C to 85°C.
The drying time is preferably 5 to 20 minutes, more preferably 5 to 15 minutes, even more preferably 5 to 13 minutes, from the viewpoint of weather resistance.

The method of applying the inorganic fine particle dispersion to the layer A is not particularly limited, but examples include brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, electro It is possible to apply a known and commonly used coating method such as a coating method.

The thickness of the C layer is not particularly limited, but from the viewpoint of abrasion resistance, boiling water resistance and weather resistance, it is preferably in the range of 7 μm to 26 μm, more preferably in the range of 8 μm to 24 μm, and 10 μm It is even more preferred to be ~15 μm.
The thickness of the C layer is determined by the same method as for the thickness of the A layer.

-Method for producing polycarbonate resin laminate with hard coat layer-
A known manufacturing method can be used as a method for manufacturing a polycarbonate resin laminate with a hard coat layer. For example, after applying a coating liquid of an inorganic fine particle dispersion to at least one surface of a polycarbonate resin layer, the coated surface is irradiated with an active energy ray such as ultraviolet rays, so that long-term weather resistance and excellent abrasion resistance in the outdoors can be obtained. It is possible to obtain a polycarbonate resin laminate with a hard coat layer that has both properties and excellent adhesion to a substrate.
Examples of the active energy rays include ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps, and usually extracted from particle accelerators of 20 kV to 2,000 kV. electron beams, α-rays, β-rays, and γ-rays.
Among them, the active energy rays are preferably ultraviolet rays or electron beams, more preferably ultraviolet rays.
By addition polymerization of the double bond in the C2 component by irradiation with active energy rays such as ultraviolet rays, the free molecular movement of the molecules constituting the hard coat layer (C layer) is suppressed, and the permeation layer (B layer) is formed. Can be immobilized.

Ultraviolet light sources include sunlight, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, argon lasers, and helium-cadmium lasers. Using these ultraviolet light sources, the coating film can be cured by irradiating the coated surface of the inorganic fine particle dispersion with ultraviolet light having a wavelength of about 180 nm to 400 nm.
The irradiation amount of ultraviolet rays is appropriately selected depending on the type and amount of the photopolymerization initiator used.
Curing with active energy rays is particularly effective when the substrate is a material with poor heat resistance such as plastic. On the other hand, when heat is used together within a range that does not affect the substrate, a known heat source such as hot air or near-infrared rays can be used.

Further, after that, the double bond in the C2 component is subjected to addition polymerization by ultraviolet irradiation, thereby restricting the free molecular movement of the molecules constituting the coating layer and fixing the permeation layer.

The laminate according to the present disclosure may be colorless or colored, but is preferably a transparent member.
The laminate according to the present disclosure preferably has a total light transmittance of 50% or more, more preferably 70% or more, measured according to JIS K7361-1 (1997) (corresponding ISO: 13468-1 1996). , more preferably 85% or more.
Since the laminate according to the present disclosure is excellent in abrasion resistance, boiling water resistance and weather resistance, it can be It can be suitably used as a transparent play board in play equipment such as. Among these, the laminate of the present disclosure can be suitably used as a vehicle glazing member.

EXAMPLES The present disclosure will be described in detail below with reference to Examples, but the present disclosure is not limited to these. In the present examples, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise specified.

<Synthesis Example 1-1: Synthesis of Polysiloxane Having Polysiloxane Segment (C1-1)>
3-Methacryloyloxypropyltrimethoxysilane (MPTS) 842.23 parts by mass and propylene glycol monomethyl ether (PGM) 842.23 parts by mass in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet. 23 parts by weight of the mixture was charged, and the temperature was raised to 60° C. while stirring under nitrogen gas ventilation. Next, a mixture of 0.44 parts by mass of "Phoslex A-4" (product name, SC Organic Chemical Co., Ltd., butyl acid phosphate) and 138.53 parts by mass of deionized water was added dropwise over 5 minutes. . After completion of the dropwise addition, the reaction vessel was heated to 80° C. and stirred for 4 hours to carry out a hydrolytic condensation reaction to obtain a reaction product. Methanol and water contained in the obtained reaction product were removed under reduced pressure of 1 kilopascal (kPa) to 30 kilopascal (kPa) under conditions of 40° C. to 60° C., thereby reducing the solid content to 60. 1013.16 parts by mass of polysiloxane having 0% by mass of polysiloxane segment (C1-1) was obtained.

<Synthesis Example 1-2: Synthesis of Composite Resin C1>
61.32 parts by mass of phenyltrimethoxysilane (PTMS) and 336.48 parts by mass of propylene glycol monomethyl ether (PGM) were charged into the same reaction vessel as in Synthesis Example 1, and while stirring under nitrogen gas ventilation, The temperature was raised to 80°C.
Then, methyl methacrylate (MMA) 125.38 parts by mass, n-butyl methacrylate (BMA) 43.98 parts by mass, cyclohexyl methacrylate (CHMA) 228.79 parts by mass, acrylic acid (AA) parts by mass, n-butyl acrylate ( n-BA) 4.58 parts by mass, MPTS: 27.45 parts by mass, 2-hydroxyethyl methacrylate (HEMA) 22.88 parts by mass, PGM: 106.77 parts by mass, tert-butylperoxy-2-ethylhexa Noate (TBPEH): A mixture containing 20.59 parts by mass was added dropwise into the reaction vessel at the same temperature over 4 hours while stirring under a nitrogen gas stream.
After further stirring at the same temperature for 2 hours, 77.73 parts by mass of dimethyldimethoxysilane (DMDMS), 0.26 parts by mass of "Phoslex A-4" and 65.8 parts by mass of deionized water were added to the reaction vessel. The mixture was added dropwise over 5 minutes and stirred at the same temperature for 4 hours to advance the hydrolytic condensation reaction of PTMS, DMDMS and MPTS. Analysis of the reaction product by ¹ H-NMR revealed that almost 100% of the trimethoxysilyl groups of the silane monomer in the reaction vessel were hydrolyzed.
Then, by stirring at the same temperature for 10 hours, a reaction product with a residual amount of TBPEH of 0.1% or less was obtained. The residual amount of TBPEH was measured by an iodine titration method to confirm the residual amount.

Next, 1013.16 parts by mass of the polysiloxane obtained in Synthesis Example 1-1 was added to the reaction product and stirred for 5 minutes, followed by stirring at 80° C. for 4 hours to obtain the reaction product and the polysiloxane. A hydrolytic condensation reaction was carried out. The resulting reaction product is distilled under reduced pressure of 10 kPa to 300 kPa under conditions of 40 ° C. to 60 ° C. for 2 hours to remove the generated methanol and water, then PGM is added, and the nonvolatile content ( A composite resin C1: 4082 parts by mass was obtained, which consists of a polysiloxane segment (C1-1) having a solid content of 50.0% by mass and a vinyl polymer segment (C1-2).
In the composite resin C1, the compounding ratio of the polysiloxane segment (C1-1) was 60% by mass, and the compounding ratio of the vinyl polymer segment (C1-2) was 40% by mass.

<Synthesis Example 2: Synthesis of isocyanuric ring-containing urethane (meth)acrylate compound (C2-1)>
An isocyanate compound (manufactured by Asahi Kasei Chemicals Co., Ltd., Duranate TPA-100, NCO Content: 23.5% by mass.) 178.72 parts by mass (NCO: 1.0 mol), 1.8 parts by mass of 2,6-di-tert-butyl-4-methylphenol, 0.2 parts by mass of dibutyltin dilaurate 158.72 parts by mass of M-305 (manufactured by Toagosei Co., Ltd.) and 85.9 parts by mass of 2-hydroxy-propyl acrylate (0.66 mol) while stirring at a liquid temperature of 60 to 70 ° C. was dripped.
After the completion of the dropwise addition, the mixture was stirred at 80°C for 4 hours, and the isocyanate (NCO) group was confirmed to have disappeared from the reaction solution by infrared spectroscopy (IR) analysis to terminate the reaction. A urethane (meth)acrylate compound (C2-1) was obtained.

<<Preparation Example 1: Production of Inorganic Fine Particle Dispersion 1>>
36 parts by mass of composite resin C1 (solid content: 50 parts by mass) and 60 parts by mass of PGM-ST (manufactured by Nissan Chemical Industries, Ltd., solid content: 30 mass%) as silica fine particles C3, Toyo Co., Ltd. A dispersion was obtained using a paint shaker manufactured by Seiki Seisakusho.
32 parts by mass of the resulting dispersion, 21.38 parts by mass of the compound (C2-1) obtained in Synthesis Example 2, and M-315 (manufactured by Toagosei Co., Ltd., isocyanur 60.7 parts by mass of acid 2-hydroxyethyl-triacrylate), 5.9 parts by mass of 1,9-DA (1,9-nonanediol diacrylate manufactured by Kyoeisha Chemical Co., Ltd.) as compound (C2-3) was blended and stirred. For the obtained formulation, 4 parts by mass of Tinuvin479 (manufactured by BASF) as a triazine-based ultraviolet absorber C4, 0.1 parts by mass of BYK-377 (manufactured by BYK-Chemie) as a non-reactive surface conditioner C5, and photostability As an agent, 1.0 parts by mass of Tinuvin 123 (manufactured by BASF) and 3 parts by mass of Irgcure 819 (manufactured by BASF) are blended and stirred, and then diluted with 88.1 parts by mass of propylene glycol monomethyl ether (PGM). After stirring, an inorganic fine particle dispersion 1 was obtained.

<<Preparation Examples 2 to 30: Production of Inorganic Fine Particle Dispersions 2 to 30>>
Inorganic fine particle dispersions 2 to 30 were obtained in the same manner as in Preparation Example 1, except that the blending ratio was changed to that shown in Table 3 or Table 4.
<<Base material A>>
As a resin material, polycarbonate resin pellets (manufactured by Teijin Limited: Panlite L-1250Z (trade name)) were dried at 110° C. for 5 hours. This resin material is injection press molded using a large injection press molding machine (manufactured by Meiki Seisakusho Co., Ltd.: MDIP2100, maximum mold clamping force 33540 kN) equipped with a 4-axis parallel control mechanism, and the thickness shown in FIG. A large molding of 4 mm, 1,200 mm long and 1,000 mm wide was produced. In such a molding machine, the pellets after drying were supplied to the feeding port of the molding machine by pneumatic transportation and used for molding. A valve gate type hot runner (diameter: 8 mmφ) manufactured by HOTSYS was used as the runner. In FIG. 1, 23 represents a linear junction observed through a polarizing plate, and 24 represents a virtual reference line.

Molding conditions: cylinder temperature 310°C, hot runner set temperature 280°C, mold temperature 110°C on the movable side, 110°C on the fixed side, compression stroke 4.0 mm, movement of the mold from the intermediate clamping state to the final clamping state. The speed was 10 mm/sec and the dwell time was 150 sec. The filling of the molten resin is a cascade molding method in which injection is started from the gate portion (first filling gate) 21 in FIG. 1 and the gate portion 22 is opened after the molten resin reaches the gate portion (second filling gate) 22. I went to Mold compression was started just before filling was complete, with an overlap of 0.5 seconds. Immediately after the completion of filling, the valve gate was closed so that the molten resin did not flow back from the gate to the cylinder. The pressure during the compression process was set to 17.2 MPa, and the pressure during the holding pressure process was held at half the pressure. The movable mold parting surface was not intended to contact the stationary mold parting surface in its final advanced position. Also, in such molding, tan θ representing the amount of inclination and the amount of twist was kept at about 0.000025 or less by the four-axis parallel control mechanism.
The resulting molded article was taken out and allowed to stand for 24 hours under the conditions of a temperature of 23° C. and a relative humidity of 50% to obtain a base material A.

<<Base material B to E>>
Substrates B to E were obtained by molding under the same conditions as for substrate A, except that the viscosity average molecular weight was changed to that shown in Table 3 or Table 4 and the molding temperature was appropriately adjusted.

<Preparation of polycarbonate resin laminate with hard coat layer>
(Examples 1 to 16 and Comparative Examples 1 to 14)
The inorganic fine particle dispersion described in Table 3 or Table 4 was applied to the surface of the base material described in Table 3 or Table 4, and dried by heating under the conditions described in Table 1 or Table 2. After that, by irradiating with ultraviolet rays at the dose shown in Table 1 or Table 2 under a mercury lamp with a lamp output of 1 kW, a polycarbonate resin laminate with a hard coat layer was produced.
The thicknesses of the polycarbonate resin layer (A layer), permeation layer (B layer) and hard coat layer (C layer) in the obtained hard coat layer polycarbonate resin laminate were measured by the method described above, and are shown in Table 3 or Table 3. 4 shows the value. The obtained hard coat layer polycarbonate resin laminate was subjected to the following evaluations, and the results are shown in Tables 3 and 4.
Further, when the cross section of the obtained hard coat layer polycarbonate resin laminate was confirmed by SEM, as shown in FIG. It was confirmed that a layer (1 in FIG. 2 indicates the thickness of the C layer) was formed. Note that the A layer is shown below the B layer in FIG.
Further, when the obtained hard coat layer polycarbonate resin laminate was measured by microscopic FT-IR, it was confirmed by the method described above that the B layer contained both the components of the A layer and the C layer.

〔evaluation〕
Total light transmittance: Measured using NDH-300A manufactured by Nippon Denshoku Co., Ltd. according to JIS K7361-1 (1997) (corresponding to ISO: 13468-1 1996).

Initial haze (H): Measured using a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. The cloudiness value (H) is expressed by H=Td/Tt×100 (Td: scattered light transmittance, Tt: total light transmittance).

<Abrasion resistance>
Before the Taber abrasion test, the surface of the hard coat layer-attached polycarbonate resin laminate was polished with a Taber ST-11 abrasive wheel for 25 revolutions to prepare a test piece. The test piece after polishing is subjected to a Taber abrasion test in accordance with ASTM D1044 under conditions of a load of 500 g, 100 rotations and 500 rotations using an abrasion wheel (product name: CS-10F, manufactured by Taber). The change (ΔH) in the haze value of the surface of the polycarbonate resin laminate with a hard coat layer before and after the abrasion test was measured.
The change in haze value (ΔH) was measured using a haze meter (product name: NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) under measurement method 2, light source A. The haze value (H) indicates a value represented by H=Td/Tt×100 (Td: scattered light transmittance, Tt: total light transmittance).
The haze value (H) was measured for three test pieces with the same polishing specification, and the average value of ΔH was evaluated according to the following evaluation criteria. It can be said that the smaller the value of ΔH, the better the wear resistance, and ΔH is preferably less than 9.0.
The wear wheel used for the Taber abrasion test was the change in haze value (ΔH ) was used in the range of 0.6 to 1.0. Abraded wheels with ΔH outside the above range were not used in the test.

<Boiling water resistance>
A polycarbonate resin laminate with a hard coat layer was cut into a size of 60 mm×120 mm to prepare a test piece. The test piece was immersed in boiling water at 100°C, held for 3 hours, then removed from the boiling water, and after removing the water adhering to the surface of the test piece and left in a room temperature (25°C) environment for 2 hours, the test piece was Then, the following adhesion test was performed.

On the surface of the hard coat layer side of the test piece, 100 grids are made with a cutter knife at intervals of 1 mm, and a tape having a predetermined adhesive strength (for example, Nichiban Cellotape (registered trademark)) is pasted and fixed. After repeating the strong peeling operation three times, the number of grids remaining on the test piece was measured. The larger the number of remaining grids, the better the adhesion, and the number of grids is preferably 100.

<Weather resistance (du-cycle super-accelerated weather resistance)>
Using an accelerated weather resistance tester (manufactured by Daipla Wintes, product name: Daipla Metal Weather KW-R5TP-A) using a metal halide lamp as a light source, the three conditions of light irradiation, darkness, and condensation are continuously tested. 120 cycles (1,440 hours) were loaded on the resulting hardcoat layer injection molding.
Here, the conditions for light irradiation were illuminance of 90 mW/cm ² , black panel temperature of 63° C., relative humidity of 70%, and light irradiation for 4 hours. 70° C. and relative humidity of 90% are maintained for 4 hours. The dew condensation condition is that the black panel temperature is naturally cooled from 70° C. to 30° C. and maintained for 4 hours at a relative humidity of 98% without irradiating light. It is. Furthermore, the hard coat layer injection molded product was subjected to water shower treatment for 10 seconds each before and after dew condensation.
During the above weather resistance test, the appearance of the hard coat layer surface was visually observed after every 5 cycles, and the number of cycles (in units of 5 cycles) immediately before defects such as cracks and peeling were confirmed on the hard coat layer surface was recorded. Evaluation was performed according to the following evaluation criteria. The higher the number of cycles, the better the weather resistance.
It is preferable that no cracks, whitening, or yellowing is observed in the appearance of the hard coat layer surface, and the number of cycles is preferably 100 or more.

In Tables 3 and 4, "-" means that the corresponding component is not included. In Comparative Example 14 in Tables 2 and 4, "PC substrate cannot be molded" means that substrate D could not be formed.
In Tables 3 and 4, the numerical values (% by mass) of C1, C2 and C3 mean the compounding ratios in the total amount of C1, C2 and C3, respectively.
In Tables 3 and 4, the numerical value (% by mass) of C3 means the blending ratio with respect to the total mass of the solid content of C1.
In Tables 3 and 4, the numerical values (% by mass) of C1-1, C2-1 and C2-3 mean the blending ratio in the total amount of C1-1, C2-1 and C2-3 respectively. there is
In Tables 3 and 4, the numerical values (% by mass) of C4 and C5 mean the amounts of C1, C2 and C3, respectively, per 100 parts by mass in total.

The details of each component in Tables 3 and 4, which are not explained above, are shown below.
・MEK: methyl ethyl ketone ・IPA: isopropyl alcohol ・Triazole-based UV absorber: Tinuvin384-2 (NV80%), manufactured by BASF Japan Ltd. ・Reactive surface conditioner: BYK-UV3505, manufactured by BYK-Chemie

It can be seen that the hard coat layer-attached polycarbonate resin laminates of Examples 1-16 are superior in weather resistance to the hard coat layer-attached polycarbonate resin laminates of Comparative Examples 1-14. Furthermore, it can be seen that the hard coat layer-attached polycarbonate resin laminates of Examples 1 to 16 are superior in wear resistance and boiling water resistance as compared to the hard coat layer-attached polycarbonate resin laminates of Comparative Examples 1 to 14. . Further, the hard coat layer-attached polycarbonate resin laminates of Examples 1 to 16 can keep the haze value low and are excellent in total light transmittance.

The disclosure of Japanese Patent Application No. 2019-140244 filed on July 30, 2019 is incorporated herein by reference in its entirety.
All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually noted to be incorporated by reference. incorporated herein by reference.

Claims (5)

A permeation layer (B layer) and a hard coat layer (C layer) are laminated in this order on at least one surface of a polycarbonate resin substrate layer (A layer) having a thickness of 1 mm to 20 mm, and the A layer, The B layer and the C layer satisfy the following requirements (a) to (e),
The B layer is in contact with the A layer and the C layer,
A polycarbonate resin laminate with a hard coat layer.
(a) The polycarbonate resin substrate layer contains a polycarbonate resin having a viscosity average molecular weight of 17,000 to 40,000.
(b) The B layer contains both the A layer and the C layer.
(c) The total thickness of the B layer and the C layer is 16 μm to 32 μm.
(d) The thickness of the layer B is 6 μm to 9 μm.
(e) The C layer satisfies the following (A) to (I).
(A) A composition containing inorganic fine particles in which the layer C contains a composite resin C1, a (meth)acrylate compound C2, silica fine particles C3, a triazine-based ultraviolet absorber C4, and a non-reactive silicone surface conditioner C5. A hard coat layer that is a cured product of
The composite resin C1 has a structural unit represented by the following formula (1) and / or the following formula (2), a polysiloxane segment (C1-1) having a silanol group and / or a hydrolyzable silyl group, A composite resin in which a vinyl polymer segment (C1-2) is bonded by a bond represented by the following formula (3).

In the above formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH=CH ₂ , -R ⁴ -C(CH ₃ )=CH ₂ , -R ⁴ A group having at least one polymerizable double bond selected from the group consisting of —O—CO—C(CH ₃ )=CH ₂ and —R ⁴ —O—CO—CH=CH ₂ (provided that R ⁴ represents a single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or a group having 7 to 12 aralkyl groups, and at least one of R ¹ , R ² and R ³ represents the group having the polymerizable double bond.

In general formula (3), a carbon atom represents a partial structure of (C1-2), and Si ^* represents a partial structure of (C1-1).
(B) The compounding ratio of the composite resin C1 is 5% by mass to 15% by mass with respect to the total amount of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3.
(C) the content of the polysiloxane segment (C1-1) in the composite resin C1 is 55% by mass to 65% by mass with respect to the total solid content of the composite resin C1;
(D) the (meth)acrylate compound C2 is an isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) represented by the following general formula (4);
an isocyanuric ring-containing tri(meth)acrylate compound (C2-2) represented by the following general formula (5);
and an aliphatic di(meth)acrylate compound (C2-3).

In general formula (4), R ⁵ , R ⁶ and R ⁷ each independently represent a group represented by formula (4-a) or formula (4-b) below.

In the above formula (4-a), n1 represents an integer of 2 to 4, R ⁸ represents a hydrogen atom or a methyl group, Q ¹ and Q ² each independently represent a hydrogen atom or a represents an alkyl group, and at least one of Q ¹ and Q ² represents an alkyl group.

In general formula (5) above, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a group represented by formula (5-a) below.

In the above formula (5-a), n2 represents an integer of 2 to 4, R ⁸ represents a hydrogen atom or a methyl group, Q ³ and Q ⁴ are each independently a hydrogen atom or a represents an alkyl group.
(E) The blending ratio of the (meth)acrylate compound C2 is 70% by mass to 90% by mass with respect to the total amount of the composite resin C1, the (meth)acrylate compound C2 and the silica fine particles C3.
(F) the isocyanurate ring-containing urethane (meth)acrylate compound (C2-1), the isocyanurate ring-containing tri(meth)acrylate compound (C2-2) and the aliphatic di(meth)acrylate compound (C2-3) With respect to the total amount, the blending ratio of the isocyanuric ring-containing urethane (meth)acrylate compound (C2-1) is 21% by mass to 33.5% by mass, and the isocyanuric ring-containing tri(meth)acrylate compound (C2- 2) is 60% to 70% by mass, and the aliphatic di(meth)acrylate compound (C2-3) is 6.5% to 9% by mass.
(G) The blending ratio of the silica fine particles C3 is 5% by mass to 15% by mass with respect to the total amount of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3.
(H) The content of the triazine-based ultraviolet absorber C4 is 3% by mass to 5% by mass with respect to a total of 100 parts by mass of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3.
(I) The blending amount of the non-reactive silicone surface conditioner C5 is 0.05% by mass to 1% by mass with respect to a total of 100 parts by mass of the composite resin C1, the (meth)acrylate compound C2, and the silica fine particles C3. %. 2. The polycarbonate resin laminate with a hard coat layer according to claim 1, wherein the ratio of the thickness of said layer B to the total thickness of said layer B and said layer C is 20% to 50%. 3. The polycarbonate resin laminate with a hard coat layer according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin. The aliphatic di(meth)acrylate compound (C2-3) is 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, or 1,10-decanediol di(meth)acrylate. ) The polycarbonate resin laminate with a hard coat layer according to any one of claims 1 to 3, which is an acrylate. Any one of claims 1 to 4, wherein the B layer has a mixture of a peak derived from a carbonate bond and a peak derived from an acrylic ester when its cross section is analyzed using a microscopic FT-IR measurement device. 2. The polycarbonate resin laminate with a hard coat layer according to item 1.

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