JP7230411B2 - Laminates and resin films - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate and a resin film capable of imparting scratch resistance and various functions to other articles by transferring a resin layer to the surface of a molded article.

In general, plastic and metal surfaces are more susceptible to scratches than glass. Therefore, when used as a product, in plastics and metal moldings that are required to maintain surface gloss and transparency, a layer that imparts scratch resistance to the surface (hereinafter referred to as a hard coat layer ) may be provided. Furthermore, this hard coat layer may be used to impart functions other than scratch resistance, such as functions such as weather resistance, gas barrier properties, and antiblocking properties, to the molded article.

This hard coat layer is generally formed by directly applying it to the surface of the plastics or metals that make up the molded body and then curing it, or forming a hard coat layer on a plastic film in advance "Hard coat film or integrally molding the hard coat film together with the plastics or metals forming the molding.

On the other hand, when direct coating is impossible due to the heat resistance, processing temperature, and solvent resistance of the materials that make up the molded body, it is formed together with functions other than scratch resistance, such as optical function layers and design layers. Therefore, there is also a method of forming a hard coat layer on a base film different from that constituting the molded body and transferring it to the surface of the molded body. Using such a process of transferring a resin layer formed on a release film, it is also possible to manufacture a resin film or an interlayer insulating film. A resin film can also be produced by using such a process of transferring a resin layer formed on a release film.

In addition, for example, in the application of electronic equipment, a method of transferring only the hard coat layer to the surface of the molded body instead of molding the hard coat film together is also being studied in order to make the product thinner and improve the flexibility of the product form. ing.

As a method for transferring only the hard coat layer to the molded body, Patent Document 1 discloses a transfer sheet having at least a release layer, a functional layer, and an adhesive layer on one side of a base material, wherein the release layer is coated with silicon. A transfer sheet characterized by using, as a main material, a silicone acrylic resin that forms a strong cured film by forming crosslinks, and using a polydimethylsiloxane-based copolymer as a secondary material." has been proposed.

In Patent Document 2, "A transfer film obtained by sequentially laminating at least a release layer, a hard coat layer, and an adhesive layer on one surface of a base film, wherein the release layer contains 10 to 30 carbon atoms. A transfer film characterized by being an acrylic urethane resin having the following long-chain alkyl group." has been proposed.

In Patent Document 3, "A hard coat transfer film in which at least a release layer and a hard coat layer made of an ultraviolet curable resin are sequentially laminated on a plastic film, and the following (A) to (C) A hard coat transfer film characterized by satisfying all the conditions of (A) The release layer and the hard coat layer are laminated so that they are in contact with each other (B) The release layer is a thermosetting resin and a hydroxyl group-containing acrylate It is a layer consisting of

(C) The weight ratio of the hydroxyl group-containing acrylate to the thermosetting resin is 3 to 10% by weight. ' is proposed.

In Patent Document 4, "A transfer foil comprising at least a base material, a release layer provided on the base material, and a protective layer releasably provided on the release layer, The transfer foil, wherein the release layer comprises an actinic radiation-curable resin and a thermosetting resin, and the protective layer comprises an actinic radiation-curable resin." .

JP 2004-034385 A JP 2014-104705 A JP 2014-180809 A JP 2017-65017 A

Thus, the following three points are the essential problems in transferring a resin layer having a function like a hard coat layer to a molded body or in manufacturing a resin film.
1. The resin layer can be uniformly formed on the release layer without defects such as repelling.
2. The resin layer must not peel off or float from the release layer during the process until it is transferred to the molded body.
3. When the resin layer is transferred to the molded body, it can be easily peeled off at the interface with the release layer without causing tearing or zipping. As a result, the method described in the specification may be effective for the coating composition for the antireflection layer, but when applied to the coating composition for the hard coating, repelling occurs during coating, resulting in a good quality coating. It was difficult to obtain a film, and the above problems could not be achieved.

When the present inventors confirmed the techniques of Patent Documents 2 to 4, the methods described in the specifications certainly ensure that a thick hard coat layer, a primer layer, and an adhesive layer are laminated to the hard coat coating composition. Although the transferability to the molded product is good in the case of the system in which the resin layer is formed, if the resin layer becomes thin, it cannot be peeled uniformly in the plane, and the above problems cannot be achieved.

Therefore, in order to simultaneously solve the above three problems, the present inventors completed the following invention as a result of earnest research. That is, the present invention is as follows.
1) A laminate having a release layer on at least one surface of a supporting substrate and a resin layer that can be peeled off from the releasing layer in this order from the supporting substrate side, wherein the resin constituting the resin layer is The surface elasticity of the resin layer containing segments having a structure represented by Chemical Formula 1 and/or Chemical Formula 2, the resin constituting the release layer containing segments having a structure represented by Chemical Formula 3 and/or Chemical Formula 4, and the resin layer having a structure represented by Chemical Formula 1 and/or Chemical Formula 2. is 100 MPa or more and 2 GPa or less, and the surface free energy γ (mN/m) of the release layer and the surface elastic modulus E (MPa) measured by an atomic force microscope satisfy formulas 1 and 2. laminate.
Formula 1 10≤γ≤45
Formula 2 1≤E≤1,000

where R ¹ is hydrogen or a methyl group.
R ² is any one of (i) to (vi) below.
(i) a substituted or unsubstituted alkylene group (ii) a substituted or unsubstituted arylene group (iii) a substituted alkylene group having an ether group, an ester group or an amide group inside (iv) an ether group, an ester group or Unsubstituted alkylene group having an amide group (v) A substituted arylene group having an ether group, an ester group or an amide group inside (vi) An unsubstituted arylene group ^R3 having an ether group, an ester group or an amide group inside is methyl, phenyl, vinyl or hexylene.
^R4 is an alkyl group having 8 or more carbon atoms or an alkylene group having 8 or more carbon atoms.
2) The laminate according to 1), wherein the release layer has an arithmetic mean roughness Ra of 5 nm or less based on JIS R1683 (2007).
3) The laminate according to 1) or 2), wherein the receding contact angle D ^B (°) of 2-hydroxypropyl acrylate of the release layer by the expansion-contraction method satisfies the following formula 3.
Formula 3 D ^B ≤ 40
4) Any of 1) to 3), wherein the depth profile of the release layer measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) satisfies the following equations 4 and 5: The laminate according to any one of the above.
Equation 4 T ¹ _s > T ² _s
Equation 5 T ¹ ₂₅ < T ² ₂₅
T ¹ _s : intensity of Si(CH ₃ ) ⁺ fragment ions on the release layer surface T ² _s : strongest among C _n H _2n+1 O ⁺ fragment ions (n is 1 to 3) on the release layer surface Intensity T ¹ ₂₅ of ions: Si(CH ₃ ) ⁺ fragment ion intensity T ² 25 at a depth of 25 nm from the release layer surface T 2 ₂₅ : C _n H _2n+1 O ⁺ at a depth of 25 nm from the release layer surface 5) the strength of the strongest fragment ion (n is 1 to 3); Laminate as described.

where ^R5 is hydrogen or a methyl group.
R ⁶ is any one of (vii) to (xii) below.
(vii) a substituted or unsubstituted alkylene group (viii) a substituted or unsubstituted arylene group (ix) a substituted alkylene group having an ether group, an ester group or an amide group inside (x) an ether group, an ester group or An unsubstituted alkylene group having an amide group (xi) A substituted arylene group having an ether group, an ester group or an amide group inside (xii) An unsubstituted arylene group having an ether group, an ester group or an amide group inside 6) A resin film obtained by peeling the release layer and the supporting substrate from the laminate according to any one of 1) to 5).

According to the present invention, even if the resin layer formed on the release layer is a thin film, defects such as repelling are unlikely to occur in the resin layer, and there is no layer such as an adhesive layer or a protective film on the resin layer. Even in such a case, the resin layer is less likely to be peeled off from the release layer in various steps up to the transfer to the molded body, and furthermore, tearing or zipping occurs when the resin layer is transferred to the molded body. It is hard and can be peeled off easily.

1 is a cross-sectional view showing an example of the configuration of a laminate of the present invention; FIG. 1 is a cross-sectional view showing an example of the configuration of a laminate of the present invention; FIG. 1 is a cross-sectional view showing an example of the configuration of a laminate of the present invention; FIG. 1 is a cross-sectional view showing an example of the configuration of a laminate of the present invention; FIG. FIG. 4 is a cross-sectional view showing the concept of measuring the receding contact angle of 2-hydroxypropyl acrylate on the release layer surface. FIG. 2 is a schematic diagram showing the concept of measuring the receding contact angle of 2-hydroxypropyl acrylate on the release layer surface. It is an example of a graph showing the relationship between the liquid suction amount obtained by measuring the receding contact angle and the dynamic contact angle. FIG. 2 is a schematic diagram showing the concept of measuring the receding contact angle of 2-hydroxypropyl acrylate on the release layer surface. It is an example of a graph showing the relationship between the liquid suction amount obtained by measuring the receding contact angle and the dynamic contact angle.

The present inventors have found that the above problems can be solved by using a laminate in which the resin layer and the release layer have specific physical properties and specific shapes. Details are described below.

First, as shown in FIG. 1, the laminate 1 of the present invention includes a release layer 4 and a resin layer 5 that can be peeled off from the release layer on at least one surface of a support substrate 3. have in this order. The release layer may be on both sides of the support substrate 8 as in FIG. 3, a protective film 17 having an adhesive layer 18 may be attached to the surface of the resin layer 16 opposite to the surface in contact with the release layer 15. Like the laminate 20 , the functional layer 25 may be laminated on the surface of the resin layer 24 opposite to the surface in contact with the release layer 23 .

Although the details of the resin layer will be described later, it is preferable that the resin constituting the resin layer contains a segment having a structure represented by Chemical Formula 1 and/or Chemical Formula 2 described above. Details of the release layer will be described later, but it is preferable that the resin constituting the release layer contains a segment having a structure represented by Chemical Formula 3 and/or Chemical Formula 4 described above.

By including the segment having the structure of Chemical Formula 1 and/or Chemical Formula 2, both the hardness required for the resin layer and the toughness to withstand transfer can be achieved. Also, by including the segment having the structure of Chemical Formula 3 and/or Chemical Formula 4, the peel force can be adjusted to an appropriate range.

In Chemical Formula 4, R ⁴ is preferably an alkyl group with 8 or more carbon atoms or an alkylene group with 8 or more carbon atoms, more preferably 8 or more and 20 or less carbon atoms.

Whether or not the resin constituting the release layer or the resin constituting the resin layer contains segments having the structures of chemical formulas 1 to 4 can be examined by various analytical methods. A method using a mass spectrometer (TOF-SIMS) is the easiest. It can also be determined from the raw material that constitutes the release layer or the resin layer.

In the laminate of the present invention, the surface elastic modulus of the resin layer measured by an atomic force microscope is 100 MPa or more and 2 GPa or less. Further, in the laminate of the present invention, the release layer preferably has an arithmetic mean roughness Ra of 5 nm or less based on JIS R1683 (2007). When the surface elastic modulus of the resin layer is less than 100 MPa or exceeds 2 GPa, i.e., when the resin layer is extremely flexible or hard laminate, or when the release layer arithmetic mean roughness Ra exceeds 5 nm, i.e. Since the surface of the release layer is rough, the effect of the resin layer formed thereon may not be sufficiently exhibited. A specific method for measuring the arithmetic mean roughness of the release layer will be described later. As will be described later, in the present invention, the resin layer separated from the release layer is called a resin film.

In addition, it is preferable that the surface free energy γ (mN/m) of the release layer and the surface elastic modulus E (MPa) measured by an atomic force microscope satisfy a specific relationship, that is, formulas 1 and 2 described above. , more preferably satisfies the following equations 1-2 and 2-2.
Formula 1-2 20≤γ≤45
Formula 2-2 10≦E≦1,000.

In a region where the surface elastic modulus E (MPa) of the release layer as measured by an atomic force microscope is smaller or larger than the range of Formula 1 or Formula 2, deterioration in appearance quality such as cissing of the coating film during formation of the resin layer, The peeling force between the resin layer and the release layer is too low, causing the resin layer to peel off or float during the process of attaching the resin layer to the molded body, or the peeling force between the resin layer and the release layer is too high. Therefore, when the resin layer is transferred to the molded body, the resin layer may be torn, or the peeling force may be unstable, resulting in so-called "zipping" in which a peeling line remains on the resin layer. may not be possible.

The surface elastic modulus of the resin layer and release layer measured by an atomic force microscope is a compression test using a probe in a very small portion, and measures the degree of deformation due to pressing force. Therefore, a cantilever with a known spring constant is used to measure the elastic modulus of the surface of the resin layer and release layer. Details are described in the Examples section.

In addition, the surface free energy γ of the release layer is obtained by determining the static contact angle at 25 ° C with water, ethylene glycol, formamide, and diiodomethane on the surface of the release layer after peeling the resin layer from the laminate. The static contact angle and the dispersion term, polar term, and hydrogen bond term of the surface free energy of each liquid described in Non-Patent Document 2 below are combined with “Hata, Kitazaki’s Extended Hawks It was found by solving the simultaneous equations.
Non-Patent Document 1: Yasuaki Kitazaki, Toshio Hata: Japan Adhesive Association Paper, 8, (3) 131 (1972).
Non-Patent Document 2: J.P. Panzer: J.P. Colloid Interface Sci. , 44, 142 (1973). .

Furthermore, the surface properties of the release layer have ^a preferable range. It is preferably in the range of 3, and more preferably in the range of formula 3-2 below.
Equation 3-2 D ^B ≦30.

If the value of Formula 3 exceeds 40, when the resin layer is formed on the release layer, repelling or the like may occur in the coating film, and the appearance quality of the resin layer may be deteriorated. As long as the value of Equation 3 is within a range that satisfies the surface roughness and surface free energy of the release layer described above, there is no problem even if it is small, and the minimum value is 0°.

Here, the receding contact angle is one of the so-called dynamic contact angles, unlike the "static contact angle" generally called the "contact angle". The expansion-contraction method is one method of measuring this dynamic contact angle. The dynamic contact angle characterizes the shape of the liquid to be measured as it moves along the surface. The contact angle when the liquid to be measured expands is the advancing contact angle, and the contact angle when it contracts is the receding contact angle. .

The reason for using the receding contact angle as a surface characteristic in the present invention is that repellency, which is the main cause of poor appearance of the resin layer, is easily moved at the interface where the surface of the release layer covered with liquid changes to air. This is because I thought it was related to In addition, the reason why 2-hydroxypropyl acrylate was used as the measurement liquid for contact angle evaluation is that cissing occurs in the latter stage of the drying process. This is because it is suitable to use an acrylic monomer.

The details of the conditions for measuring the advancing contact angle and the receding contact angle will be described later, but the measuring method by the expansion-contraction method will be explained with reference to FIGS. 5 to 9. FIG. FIG. 5 shows the initial state of receding contact angle measurement. A liquid to be measured is supplied through a syringe needle 27 onto the release layer surface 26 to form a droplet 28 . The contact angle 29 at this time corresponds to the static contact angle.

FIG. 6 shows the measurement state of the surface of the resin layer with a high receding contact angle. When the liquid to be measured is sucked from the droplet through the syringe needle 31 at a constant flow rate, the droplet on the release layer surface 30 becomes smaller. Since the receding contact angle is high at this time, the area over which the liquid to be measured is spread becomes smaller. FIG. 7 shows changes in the contact angle at this time. The abscissa represents the measurement time or the amount of the aspirated measurement solution, and the ordinate represents the contact angle at each time point. The contact angle decreases slightly immediately after the start of measurement, but after that it becomes constant at a relatively high value. This constant value is called receding contact angle.

FIG. 8 shows the measured state of the release layer surface with a low receding contact angle. When the liquid to be measured is sucked, the droplet becomes smaller, but the edge of the droplet does not move much and the height of the droplet decreases. FIG. 9 shows changes in the contact angle at this time. The contact angle drops significantly from the start of measurement, and becomes constant when it drops. Also, depending on the sample, the receding contact angle may not be constant, and in this case the receding contact angle will be 0°. The contact angle can be measured by the expansion/contraction method using, for example, Drop Master (manufactured by Kyowa Interface Science Co., Ltd.).

Furthermore, the composition of the release layer surface has a preferable range. Specifically, in the depth profile measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), Si ( CH ₃ ) ⁺ fragment ion intensity T ¹ _s (hereinafter sometimes referred to as T ¹ _s ), the strongest among C _n H _2n+1 O ⁺ fragment ions (n is 1 to 3) on the release layer surface the intensity T ² _s (hereinafter sometimes referred to as T ² _s ) of the substance, the intensity T ¹ ₂₅ of Si(CH ₃ ) ⁺ fragment ions at a depth of 25 nm from the surface of the release layer (hereinafter referred to as T ¹ ₂₅ ) and the intensity T 2 25 of ^the strongest one among C _n H _2n+1 O ⁺ fragment ions (n is 1 to 3) at a depth of 25 nm _from the release layer surface: (hereinafter, T ² ₂₅ ) preferably satisfies Equations 4 and 5 above.

Satisfying the above formulas 4 and 5 means that the surface of the release layer is covered with dimethylsiloxane segments, but the region is extremely thin, and the inner portion has a solvent-friendly region. indicates that Dimethylsiloxane provides low peeling force due to its flexibility and low surface energy, but since the area is extremely thin, the solvent-philic area immediately below contributes to the formation of the resin layer, resulting in difficulty in repelling. It is thought that

If the above formula 4 is not satisfied, the peeling force increases, and when the resin layer is transferred to the molded body, the resin layer may be torn, or the peeling force is unstable, leaving a peeling line on the resin layer. In some cases, it may not be possible to uniformly transfer within the surface due to "zipping". If the above formula 5 is not satisfied, cissing or the like may occur and the quality of the resin layer may deteriorate.

Further, it is preferable that the resin constituting the release layer contains a segment having a structure of Chemical Formula 5. Chemical formula 5 indicates a structure that contains an unreacted acrylic group, has an ether bond at the other end, and is fixed by cross-linking with the main cross-linking component of the release layer. By containing an unreacted acrylic group, affinity can be ensured when a resin layer is formed on the release layer surface.

Whether or not the resin constituting the release layer contains the segment of chemical formula 5 can be examined by various analysis methods, but the method using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) is the most suitable. Easy. It can also be determined from the raw material that constitutes the release layer.

[Mode of the present invention]
Embodiments of the present invention will be specifically described below.

[Laminate, resin layer, resin film]
The resin layer in the present invention refers to a layer formed at least on a release layer (described later) provided on a supporting base material and which can be peeled off at the interface between the release layer and the resin layer. The criteria for judging whether or not this separation is possible are evaluated by the cross-cut method described in JIS K5600-5-6: 1999, and classification 4 or higher is peelable, and classification 0 to 3 is peelable. Impossible.

In the present invention, a layered product has a supporting substrate, a release layer, and a resin layer in this order. When only one layer is formed on the release layer, the one layer is a resin layer, and when two or more layers are formed on the release layer, the two layers excluding the release layer Let the layer more than a layer be one resin layer. Moreover, the resin layer peeled off from the supporting substrate and the release layer may be referred to as a "resin film" in order to clarify that the supporting substrate and the release layer are not included.

Here, the term "layer" refers to a portion having a boundary surface distinguishable from adjacent portions in the thickness direction and having a finite thickness in the thickness direction from the surface side of the laminate. More specifically, when the cross section of the laminate is observed with an electron microscope (transmission type, scanning type) or an optical microscope, it refers to the presence or absence of discontinuous boundary surfaces. Therefore, even if the compositions of the resin layer and the release layer change in the thickness direction, if there is no interface between them, they are treated as one layer.

As described above, the resin constituting the resin layer contains a segment having a structure of chemical formula 1 and / or chemical formula 2, and if the surface elastic modulus by atomic force microscope can satisfy the above range, the material is Although not particularly limited, it is preferable to form the resin layer coating composition described later on the surface of the supporting substrate by applying, drying and curing the resin layer manufacturing method described later.

The resin layer may be composed of a plurality of layers, and the thickness thereof is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less. The resin layer has glossiness, fingerprint resistance, moldability, designability, scratch resistance, stain resistance, solvent resistance, antireflection, antistatic, conductivity, heat reflection, near-infrared absorption, electromagnetic wave shielding, and easy adhesion. You may have other functions, such as.

[Release layer]
The release layer in the present invention is located between the supporting substrate and the resin layer in the laminate and is in contact with the supporting substrate and the resin layer. From the viewpoint of imparting adhesion, antistatic properties, solvent resistance, etc., the release layer may be composed of a plurality of layers, and may be present on both sides of the support substrate.

The thickness of the release layer is not particularly limited as long as the surface in contact with the resin layer can have the surface elastic modulus E measured by the atomic force microscope described above. is preferably from 10 to 500 nm, more preferably from 20 to 300 nm.

The release layer contains a segment having a structure represented by chemical formula 3 and/or chemical formula 4, and the surface free energy γ and the surface elastic modulus E measured by an atomic force microscope satisfy the ranges described above. If possible, the material is not particularly limited, but it is preferably formed from the release layer coating composition described later, and the support substrate is formed by coating, drying, and curing according to the release layer manufacturing method described later. It is preferably formed on the surface.

[Support base material]
The supporting substrate used in the laminate of the present invention may be composed of either a thermoplastic resin or a thermosetting resin, may be a homoresin, may be a copolymer or a blend of two or more. good too. It is preferable that the resin constituting the supporting substrate has good moldability into a film form, and from this point, it is more preferable to use a thermoplastic resin that can be formed into a film by melt or a resin that can be formed into a film from a solution.

Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyimide resins, polyester resins, polycarbonate resins, Fluorine such as polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluoroethylene chloride resin, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride resin, etc. Resins, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. Examples of thermosetting resins that can be used include phenol resins, epoxy resins, urea resins, melamine resins, unsaturated polyester resins, polyurethane resins, polyimide resins, and silicone resins. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. From the viewpoint of strength, heat resistance, and transparency, the thermoplastic resin is more preferably polyester resin, polycarbonate resin, acrylic resin, or methacrylic resin.

The polyester resin in the present invention is a general term for polymers having an ester bond as a main linking chain, and is obtained by polycondensation of an acid component, its ester, and a diol component. Specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene terephthalate. In addition, other dicarboxylic acids and their esters or diol components may be copolymerized with these as acid components or diol components. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferred in terms of transparency, dimensional stability and heat resistance.

Examples of resins that can be formed into a solution film include cellulose esters (triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, nitrocellulose) and the like, and triacetyl cellulose is particularly preferred.

Various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant or the like for adjusting the refractive index may be added. The supporting substrate may have either a single-layer structure or a laminated structure.

Various surface treatments may be applied before forming the resin layer. Examples of surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred. In addition, the surface of the supporting base material may be previously provided with a plurality of functional layers such as an easy-adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorbing layer.

[Laminate]
The laminate in the present invention refers to at least the release layer and the resin layer described above in this order from the support substrate side, and one or more layers may be further formed on the resin layer, For example, a functional layer, an adhesive layer, an electronic circuit layer, a printing layer, an optical adjustment layer, etc., having the above functions, or other functional layers may be provided, and as described above, the surface of the resin layer not in contact with the release layer In addition, a protective film may be attached.

[Laminate production method]
The method for producing the laminate of the present invention is not particularly limited as long as the release layer and the resin layer satisfying the above conditions can be formed on the support base material. A layer coating composition is applied, dried, and if necessary cured to form a release layer, and then the resin layer coating composition is applied onto the release layer of the supporting substrate provided with the release layer. , drying and, if necessary, curing to form a resin layer.

The coating method is not particularly limited as long as the coating composition for the release layer or the coating composition for the resin layer can be applied onto the support substrate or the release layer to form a uniform coating layer in the plane. The coating method on the film can be appropriately selected from a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method (US Pat. No. 2,681,294), and the like. Here, the coating layer refers to a "liquid layer" formed by a coating process.

The drying method is not particularly limited as long as the solvent can be removed from the coating layer formed on the support substrate or the release layer. Examples of the drying method include heat transfer drying (adhesion to a high-temperature object), convective heat transfer (hot air), radiant heat transfer (infrared rays), and others (microwaves, induction heating). In the manufacturing method of (1), a method using convective heat transfer or radiant heat transfer is preferable because it is necessary to precisely uniform the drying speed even in the width direction.

The curing method is to irradiate the release layer or resin layer with heat or energy rays after drying to cause a reaction and cure the coating film. In the curing step, when curing is performed by heat, the temperature is preferably from room temperature to 200°C, more preferably from 100°C to 200°C, still more preferably from 130°C to 200°C, from the viewpoint of the activation energy of the curing reaction. Although it is the following, it may serve as a drying process, and may be performed continuously.

When curing with energy rays, electron rays (EB rays) and/or ultraviolet rays (UV rays) are preferred from the viewpoint of versatility. Further, the types of ultraviolet lamps used for irradiating ultraviolet rays include, for example, a discharge lamp method, a flash method, a laser method, an electrodeless lamp method, and the like. When ultraviolet curing is performed using a discharge lamp type high-pressure mercury lamp, the ultraviolet illuminance is preferably 100 to 3,000 (mW/cm ² ), more preferably 200 to 2,000 (mW/cm ² ), still more preferably. ^{is preferably 300 to 1,500 (mW/cm 2 )} . It is preferable to irradiate ultraviolet rays under the condition of 2,000 (mJ/cm ² ), more preferably 300 to 1,500 (mJ/cm ² ). Here, the illuminance of ultraviolet rays is the irradiation intensity received per unit area, and varies depending on the lamp output, the emission spectrum efficiency, the diameter of the light-emitting bulb, the design of the reflecting mirror, and the distance from the light source to the irradiated object. However, the illuminance does not change with the transport speed. Further, the cumulative amount of ultraviolet light is the irradiation energy received per unit area, and is the total amount of photons that reach the surface. The integrated amount of light is inversely proportional to the irradiation speed passing under the light source, and proportional to the number of times of irradiation and the number of lamp lights.

[Release layer coating composition]
When the release layer is formed on the supporting substrate by the above-described laminate manufacturing method, the release layer contains the above-described segments and has the above-described arithmetic mean roughness Ra, The material is not particularly limited as long as it satisfies the surface elastic modulus and surface free energy measured by an atomic force microscope, but a silicone resin or an organic resin-modified silicone resin having a reactive site and a polyalkylene oxide having a reactive site can be used. and an organic resin component capable of reacting therewith.

As the silicone-based resin having a reactive site, polydimethylsiloxane modified at the reactive site or silicone oligomer modified at the reactive site is preferable. Modification sites may be side chains of polymers, oligomers, both ends, or one end. Reactive sites include amino, epoxy, carbinol, diol, mercapto, carboxyl, phenol, silanol, (meth)acryl, and carboxylic acid anhydride. The molecular weight of the dimethylsiloxane portion and the functional group equivalent weight of the modification site, which will be described later, are appropriately selected.

Organic resin-modified silicone resins are used to adjust the viscoelasticity and surface free energy of silicone-based resins, and include silicone resins modified with resins such as epoxy, alkyd, and polyester.

Examples of resins containing polyalkylene oxide include polyols containing alkylene oxide segments and modified polyols modified with reactive sites such as (meth)acrylate, epoxy, and carboxylic acid. Further, modified polydimethylsiloxane in which polyether serves as a reactive site, etc., can be cited as examples of those integrated with the aforementioned silicone resin.

Organic resins that can react with the above materials are not particularly limited, and include acrylic resins such as acrylic polyol, polyesters such as alkyd resins, epoxy resins, and urethane resins.

[Coating composition for resin layer]
The method for producing the laminate of the present invention is not particularly limited, but the laminate of the present invention is obtained, for example, by applying a coating composition to at least one of the supporting substrates described above, and drying and curing as necessary. be able to.

Here, the "coating composition" is a liquid consisting of a solvent and a solute, and is applied to the above-mentioned supporting substrate, and the solvent is volatilized, removed, and cured in the drying process to form a resin layer. point to Here, the “type” of the coating composition refers to liquids in which even a part of the type of solute that constitutes the coating composition is different. This solute includes resins or materials capable of forming them in the coating process (hereafter referred to as precursors), particles, and polymerization initiators, curing agents, catalysts, leveling agents, UV absorbers, antioxidants, etc. Consists of various additives.

[Binder Raw Material for Resin Layer Coating Composition]
The binder raw material refers to a material that is soluble in a solvent, can be included in the coating composition, and can cure the coating film by volatilization of the solvent and its own polymerization and crosslinking reaction, and the state after curing is called a binder. call. At least one of the two or more types of coating compositions used in the method for producing a laminate of the present invention preferably contains a binder raw material, and all of the above two types of coating compositions contain a binder raw material. is more preferred. The binder raw material is not particularly limited, but may be of one type or a mixture of two or more types.

Further, in the above-described method for producing a laminate of the present invention, the binder raw material is polymerized by an active energy ray, by itself or in combination with a photopolymerization initiator that can be cleaved by an active energy ray, and the coating film can be cured. materials are preferred.

Specifically, when ultraviolet light is used as the active energy ray and a photopolymerization initiator is used in combination, preferred binder raw materials are polyfunctional (meth)acrylate monomers, (meth)acrylate oligomers, and (meth)acrylic group-containing alkoxysilanes. , (meth)acrylic group-containing alkoxysilane hydrolyzate, (meth)acrylic group-containing alkoxysilane oligomer, (meth)acrylic group-containing acrylic polymer, (meth)acrylic group-containing urethane polymer, (meth) They are an epoxy-based polymer having an acrylic group and a silicone-based polymer having a (meth)acrylic group.

Examples of polyfunctional acrylate monomers include polyfunctional acrylates having two or more (meth)acryloyloxy groups in one molecule and modified polymers thereof, specific examples include pentaerythritol tri(meth)acrylate and pentaerythritol Tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate , pentaerythritol triacrylate, hexanemethylene diisocyanate urethane polymer, and the like can be used. These monomers can be used singly or in combination of two or more.

Examples of commercially available polyfunctional acrylic compositions include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” (registered trademark) series), Nagase & Co., Ltd. (trade name “Denacol” (registered trademark) series etc.), Shin-Nakamura Chemical Co., Ltd.; (trade name “NK Ester” series, etc.), DIC Corporation; series, etc.), NOF Corporation; (“Brenmer” (registered trademark) series, etc.), Nippon Kayaku Co., Ltd.; Light Ester" series, etc.) can be mentioned, and these products can be used.

Acrylic polymers having (meth)acrylic groups are preferably synthesized by polymerization reaction of polyfunctional acrylate monomers (eg, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of urethane-based polymers include melamine polyurethane. As the silicone-based polymer, a cohydrolyzate of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy, methacryl) is preferably used. Further, various polymers that do not contain unsaturated groups, have a weight average molecular weight of 5,000 to 200,000, and a glass transition temperature of 20 to 200° C. can be used.

[Particle material and particle component for coating composition for resin layer]
The resin layer of the laminate of the present invention may contain a particle component. Here, the particles may be either inorganic particles or organic particles, but inorganic particles are preferred from the viewpoint of scratch resistance.

The number of types of inorganic particles is preferably 1 or more and 20 or less. The number of types of inorganic particles is more preferably 1 to 10, and particularly preferably 1 to 4. Here, the term "inorganic particles" includes those subjected to surface treatment. This surface treatment means introducing a compound to the particle surface by chemical bonding (including covalent bonding, hydrogen bonding, ionic bonding, van der Waals bonding, hydrophobic bonding, etc.) or adsorption (including physical adsorption and chemical adsorption). Point.

Here, the type of inorganic particles is determined by the types of elements that constitute the inorganic particles, and in the case of performing some surface treatment, it is determined by the types of elements that constitute the particles before surface treatment. For example, titanium oxide (TiO2) and nitrogen-doped titanium oxide (TiO _2-x N _x ) obtained by substituting part of the oxygen of titanium oxide with nitrogen, which is an anion, are different because the elements constituting the inorganic particles are different. It is a kind of inorganic particles. In addition, in the case of particles (ZnO) composed only of the same element, for example, Zn and O, even if there are a plurality of particles with different number average particle diameters, and even if the composition ratio of Zn and O is different, These are particles of the same kind. Even if there are a plurality of Zn particles with different oxidation numbers, as long as the elements constituting the particles are the same (in this example, as long as all the elements other than Zn are the same), they are the same type of particles. .

Here, the particles present in the coating composition used in the present invention are "particulate material", and the coating composition is present in the resin layer formed by coating, drying, curing treatment or vapor deposition. The particles are called "particle components".

The inorganic particles are not particularly limited, but are preferably oxides, nitrides, borides, chlorides, carbonates, and sulfates of metals and semimetals, and composite oxides containing two kinds of metals and semimetals, A different element may be introduced between lattices, lattice points may be replaced with a different element, or lattice defects may be introduced.

The inorganic particles are oxide particles obtained by oxidizing at least one metal or semimetal selected from the group consisting of Si, Al, Ca, Zn, Ga, Mg, Zr, Ti, In, Sb, Sn, Ba and Ce. is more preferred.

Specifically, silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), and at least one metal oxide or metalloid oxide selected from the group consisting of indium tin oxide (In ₂ O ₃ ). Silica (SiO ₂ ) is particularly preferred.

[solvent]
The coating composition for the release layer and the coating composition for the resin layer of the present invention may contain a solvent, and it is preferable to contain the solvent in order to uniformly form the coating layer in the plane. The number of types of solvents is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 4.

As used herein, the term "solvent" refers to a substance that is liquid at normal temperature and normal pressure and that can be almost completely evaporated in the drying process described above.

Here, the type of solvent is determined by the molecular structure that constitutes the solvent. That is, even if the elemental composition is the same and the type and number of functional groups are the same, the bonding relationship is different (structural isomers). Those that do not overlap exactly (stereoisomers) are treated as different kinds of solvents. For example, 2-propanol and n-propanol are treated as different solvents.

Furthermore, when a solvent is included, the solvent preferably exhibits the following characteristics.

[Other components in the coating composition]
Further, the release layer coating composition and the resin layer coating composition of the present invention preferably contain a polymerization initiator, a curing agent and a catalyst. Polymerization initiators and catalysts are used to accelerate the curing of the resin layer. As the polymerization initiator, those capable of initiating or promoting the polymerization, condensation or crosslinking reaction of components contained in the coating composition by anionic, cationic or radical polymerization reactions are preferred.

Various polymerization initiators, curing agents and catalysts can be used. The polymerization initiator, curing agent and catalyst may be used singly, or multiple polymerization initiators, curing agents and catalysts may be used simultaneously. Furthermore, an acidic catalyst or a thermal polymerization initiator may be used in combination. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid, and the like. Examples of thermal polymerization initiators include peroxides and azo compounds. Examples of photopolymerization initiators include alkylphenone-based compounds, sulfur-containing compounds, acylphosphine oxide-based compounds, and amine-based compounds. Examples of cross-linking catalysts that promote the formation reaction of urethane bonds include dibutyltin dilaurate and dibutyltin diethylhexoate.

In addition, the coating composition may contain other cross-linking agents such as melamine cross-linking agents such as alkoxymethylolmelamine, acid anhydride-based cross-linking agents such as 3-methyl-hexahydrophthalic anhydride, and amine-based cross-linking agents such as diethylaminopropylamine. It is also possible to include

As the photopolymerization initiator, an alkylphenone-based compound is preferable from the viewpoint of curability. Specific examples of alkylphenone-type compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-phenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1-(4-phenyl)-1-butane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl ) methyl]-1-[4-(4-morpholinyl)phenyl]-1-butane, 1-cyclohexyl-phenylketone, 2-methyl-1-phenylpropan-1-one, 1-[4-(2-ethoxy )-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2-phenyl-2-oxoacetic acid)oxybisethylene, and high molecular weight products of these materials. .

Further, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like may be added to the coating composition for the release layer and the coating composition for the resin layer as long as the effects of the present invention are not impaired. Thereby, the release layer and the resin layer can contain a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like. Examples of leveling agents include acrylic copolymers, silicone-based leveling agents, and fluorine-based leveling agents. Specific examples of UV absorbers include benzophenone, benzotriazole, oxalic acid anilide, triazine, and hindered amine UV absorbers. Examples of antistatic agents include metal salts such as lithium, sodium, potassium, rubidium, cesium, magnesium and calcium salts.

[Use]
The laminate of the present invention can be suitably used for moldings made of plastics or metals, for example, by taking advantage of the appearance quality of the surface and the ease of handling up to transfer. Furthermore, the resin film obtained by peeling the release layer and the supporting substrate from the laminate of the present invention can be suitably used, for example, as a protective film for molded articles.

EXAMPLES Next, the present invention will be described based on Examples, but the present invention is not necessarily limited to these. In addition, hereinafter, Example 11 shall be read as Reference Example 11.

[Release layer coating composition 1]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition 1 having a solid content concentration of 5% by mass.
・Side chain type carbinol-modified reactive silicone oil (X-22-4015 Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 5 parts by mass ・Both end-type polyether-modified reactive silicone oil (X-22-4952 Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 5 parts by mass Acryl-modified alkyd resin solution (Hariftal KV-905 Harima Chemicals Co., Ltd. solid content concentration 53% by mass): 100 parts by mass Isobutyl alcohol-modified melamine resin solution ( Melan 2650L Hitachi Chemical Co., Ltd. Solid content concentration 60% by mass): 20 parts by mass Para-toluenesulfonic acid: 5 parts by mass.

[Release layer coating composition 1-2]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition 1-2 with a solid content concentration of 5% by mass.
・Side chain type carbinol-modified reactive silicone oil (X-22-4015 Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 5 parts by mass ・Both end-type polyether-modified reactive silicone oil (X-22-4952 Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 5 parts by mass Acryl-modified alkyd resin solution (Hariftal KV-905 Harima Chemicals Co., Ltd. solid content concentration 53% by mass): 100 parts by mass Isobutyl alcohol-modified melamine resin solution ( Melan 2650L Hitachi Chemical Co., Ltd. Solid content concentration 60% by mass): 20 parts by mass 4-hydroxybutyl acrylate: 5 parts by mass Para-toluenesulfonic acid: 5 parts by mass.

[Release layer coating composition 1-3]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition 1-3 with a solid concentration of 5% by mass.
・Side chain type carbinol-modified reactive silicone oil (X-22-4015 Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 5 parts by mass ・Both end-type polyether-modified reactive silicone oil (X-22-4952 Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 5 parts by mass Acryl-modified alkyd resin solution (Hariftal KV-905 Harima Chemicals Co., Ltd. solid content concentration 53% by mass): 100 parts by mass Isobutyl alcohol-modified melamine resin solution ( Melan 2650L Hitachi Chemical Co., Ltd. Solid content concentration 60% by mass): 20 parts by mass Hydroxypropyl acrylate: 5 parts by mass Paratoluenesulfonic acid: 5 parts by mass.

[Release layer coating composition 2]
The following materials were mixed and diluted with a mixed solvent of toluene/heptane (mixing ratio by mass: 50/50) to obtain a release layer coating composition 2 having a solid concentration of 2% by mass.
・Toluene solution of methylvinylpolysiloxane and methylhydrogenated polysiloxane (LTC752 Coating manufactured by Dow Corning Toray Co., Ltd. solid content concentration 30% by mass): 95 parts by mass ・Heavy release additive (BY24-4980 Toray Dow Corning ( Co., Ltd. Solid content concentration 30% by mass): 5 parts by mass Methylvinylpolysiloxane and platinum complex solution (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.1 part by mass.

[Release layer coating composition 3]
The following materials were mixed and diluted with a mixed solvent of toluene/heptane (mixing ratio by mass: 50/50) to obtain a release layer coating composition 3 having a solid concentration of 2% by mass.
・Toluene solution of methylvinylpolysiloxane and methylhydrogenated polysiloxane (LTC752 Coating manufactured by Dow Corning Toray Co., Ltd. Solid content concentration 30% by mass): 85 parts by mass ・Peeling additive (BY24-4980 Dow Corning Toray Co., Ltd.) ) Solid content concentration 30% by mass): 5 parts by mass Methylvinylpolysiloxane and platinum complex solution (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.1 part by mass.

[Release layer coating composition 4]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition 4 having a solid content concentration of 5% by mass.
・ Single-end carbinol-modified reactive silicone oil (X-22-170DX Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 5 parts ・ Both-end polyether-modified reactive silicone oil (X-22-4952 Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 5 parts by mass Acryl-modified alkyd resin solution (Hariftal KV-905 Harima Chemicals Co., Ltd. solid content concentration 53% by mass): 100 parts by mass Isobutyl alcohol-modified melamine resin solution ( Melan 2650L Hitachi Chemical Co., Ltd. Solid content concentration 60% by mass): 20 parts by mass Para-toluenesulfonic acid: 5 parts by mass.

[Release layer coating composition 5]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition 5 having a solid content concentration of 5% by mass.
・Toluene/xylene/isobutanol/methanol mixed solution of long-chain alkyl group-containing amino alkyd resin (manufactured by Hitachi Chemical Co., Ltd., Tesfine ^R 305, solid content concentration 50% by mass)
[Release layer coating composition 6]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition 5 having a solid content concentration of 5% by mass.
・Single-end carbinol-modified reactive silicone oil (X-22-170DX Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 1 part by mass ・Double-end polyether-modified reactive silicone oil (X-22-4952 Shin-Etsu Chemical Co., Ltd. effective content 100% by mass): 5 parts by mass Acryl-modified alkyd resin solution (Hariftal KV-905 Harima Chemicals Co., Ltd. solid content concentration 53% by mass): 100 parts by mass Isobutyl alcohol-modified melamine resin solution ( Melan 2650L Hitachi Chemical Co., Ltd. Solid content concentration 60% by mass): 20 parts by mass Para-toluenesulfonic acid: 5 parts by mass.

[Release layer coating composition 7]
The following materials were mixed and diluted with a toluene/heptane mixed solvent (mixing ratio by mass: 50/50) to obtain a release layer coating composition 7 having a solid concentration of 2% by mass.
・Toluene solution of methylvinylpolysiloxane and methylhydrogenated polysiloxane: 10 parts by mass (KS847H manufactured by Shin-Etsu Chemical Co., Ltd. solid content concentration 30% by mass)
・ Complex solution of methylvinylpolysiloxane and platinum: 0.1 parts by mass (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.)
- Toluene: 10 parts by mass - Heptane: 10 parts by mass.

[Release layer coating composition 8]
The following materials were mixed and diluted with a toluene/isopropyl alcohol mixed solvent (mixing ratio by mass: 20/10) to obtain a release layer coating composition 8 having a solid concentration of 4% by mass.
・ Toluene solution of a mixture of long-chain alkyl urethane acrylate and polyfunctional acrylate monomer (TA37-400A manufactured by Hitachi Chemical Co., Ltd. solid content concentration 50% by mass): 3 parts by mass ・ α hydroxyacetophenone type photopolymerization initiator (Irgacure 184 BASF Japan Co., Ltd.): 3 parts by mass.

[Release layer coating composition 9]
The following materials were mixed and diluted with a toluene/cyclohexanone mixed solvent (mixing ratio by mass: 50/50) to obtain a release layer coating composition 9 having a solid concentration of 2% by mass.
・Butyl melamine formaldehyde paint (RP-50 Co., Ltd. Miwa Laboratory): 20 parts by mass ・Alkyl-modified polyurethane resin (RP-20 Co., Ltd. Nippon Shokubai): 0.3 parts by mass ・Phosphite ester ( Plus Coat DEP Clear (manufactured by Wasin Chemical Industry Co., Ltd.): 4 parts by mass.

[Preparation of coating composition for resin layer]
[Resin layer coating composition 1]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 1 having a solid content concentration of 30% by mass.
・Butyl acetate / ethyl acetate solution of polymer acrylate resin: 190 parts by mass ("Unidic" V-6850 DIC Corporation solid content concentration 50% by mass)
・ Urethane acrylate oligomer (“Shiko” UV3200B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass): 5 parts by mass ・ α-Hydroxyacetophenone type photopolymerization initiator: 3.0 parts by mass (“Irgacure” (registered trademark) ) 184 manufactured by BASF Japan Ltd.).

[Resin layer coating composition 2]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 2 having a solid content concentration of 30% by mass.
・Butyl acetate / ethyl acetate solution of polymer acrylate resin: 200 parts by mass ("Unidic" V-6850 DIC Corporation solid content concentration 50% by mass)
- α-Hydroxyacetophenone-type photopolymerization initiator: 3.0 parts by mass (“Irgacure” (registered trademark) 184, manufactured by BASF Japan Ltd.).

[Resin layer coating composition 3]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 3 having a solid content concentration of 30% by mass.
・Butyl acetate / ethyl acetate solution of polymer acrylate resin: 180 parts by mass ("Unidic" V-6850 DIC Corporation solid content concentration 50% by mass)
・ Urethane acrylate oligomer (“Shiko” UV3200B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass): 10 parts by mass ・ α-Hydroxyacetophenone type photopolymerization initiator: 3.0 parts by mass (“Irgacure” (registered trademark) ) 184 manufactured by BASF Japan Ltd.).

[Preparation of release layer-attached support substrates 1 to 9]
Using the release layer coating composition and the supporting substrate described above, a releasing layer was formed using the following method to prepare a supporting substrate with a releasing layer. Table 1 shows the combination of the coating composition for the release layer to be used, the method for forming the release layer, and the thickness of the release layer.

[Formation of release layer 1]
Using a coating device having a small-diameter gravure coater, a 50 μm-thick polyester film (trade name “Lumirror” (registered trademark) R75X manufactured by Toray Industries, Inc.) is coated with a coating composition for a release layer as shown in Table 1. The number of gravure lines, the peripheral speed, and the solid content concentration are adjusted so as to obtain a thickness, and then the coating is applied, and then held at a hot air temperature of 140° C. for 30 seconds to dry and cure, thereby forming a support substrate with a release layer. Obtained.

[Formation of release layer 2]
Using a coating device having a small-diameter gravure coater, a 50 μm-thick polyester film (trade name “Lumirror” (registered trademark) R75X manufactured by Toray Industries, Inc.) is coated with a coating composition for a release layer as shown in Table 1. The number of gravure lines, the peripheral speed, and the solid content concentration are adjusted so as to obtain a thickness, and then the coating is applied, and then held at a hot air temperature of 120° C. for 30 seconds to dry and cure, thereby forming a support substrate with a release layer. Obtained.

[Formation of release layer 3]
Using a coating device having a small-diameter gravure coater, a 50 μm-thick polyester film (trade name “Lumirror” (registered trademark) R75X manufactured by Toray Industries, Inc.) is coated with a coating composition for a release layer as shown in Table 1. The number of gravure lines, the peripheral speed ^, and the solid content concentration are adjusted so as to obtain a thickness, and the coating is applied. Curing was carried out by irradiating with a high-pressure mercury lamp under the condition that the integrated amount of light was 120 mJ/cm ² to obtain a support substrate with a release layer.

[Formation of release layer 4]
Using a coating device having a small-diameter gravure coater, a release layer coating composition was applied to a 50 μm-thick triacetyl cellulose film (manufactured by IPI) so that the release layer thickness shown in Table 1 was obtained. The peripheral speed and the solid content concentration were adjusted for coating, followed by drying and curing by holding at a hot air temperature of 140° C. for 30 seconds to obtain a release film.

[Preparation of laminate]
A laminate was prepared by forming a resin layer using the above coating composition for a resin layer and a support substrate with a release layer. Table 1 shows the combination of the coating composition for the resin layer to be used, the method for forming the resin layer, and the thickness of the resin layer.

[Formation of resin layer]
Using a continuous coating device having a single-layer slot die coater, the above-mentioned resin layer coating composition is applied to the above-mentioned support substrate with a release layer so that the resin layer thickness shown in Table 1 is obtained. Apply by adjusting the discharge flow rate, then dry by holding at a hot air temperature of 80 ° C. for 30 seconds, then oxygen partial pressure of 0.1% by volume or less, ultraviolet illuminance of 400 W / cm ² , and the integrated amount of ultraviolet light Curing was performed by irradiating with a high-pressure mercury lamp under conditions of 120 mJ/cm ² to form a resin layer.

[Physical Property Evaluation of Laminate]
The laminates produced in Examples 1 to 12 and Comparative Examples 1 to 3 were subjected to the physical property evaluation shown below, and the obtained results are summarized in Tables 2 and 3. Unless otherwise specified, the measurement was performed three times for each sample in each example and comparative example at different locations, and the average value was used. Further, whether or not the release layer and the resin layer contain segments having structures represented by chemical formulas 1 to 5 and whether or not the segments have the structures represented by chemical formulas 1 to 5 are described.

[Measurement of arithmetic mean roughness Ra of release layer based on JIS R1683 (2007)]
The surface of the release layer was measured using the following equipment and conditions to determine the center line average roughness Ra specified in JIS R1683 (2007).
Measuring device: Burker Corporation atomic force microscope (AFM)
Measurement mode: Tapping mode Cantilever: SCANASYST-AIR manufactured by Bruker AXS
(Material: Si, spring constant K: 0.4 (N/m), tip curvature radius R: 2 (nm))
Measurement atmosphere: 23°C, atmospheric measurement range: 3 (μm) square resolution: 512×512.

[Measurement of surface elastic modulus E of resin layer and release layer by atomic force microscope]
Measurement of the surface elastic modulus of the resin layer by an atomic force microscope and the surface elastic modulus E of the release layer are performed using AFM (DimensionIcon manufactured by Burker Corporation) in PeakForceQNM mode, and the resulting force curve is attached. Analysis based on the JKR contact theory was performed using the analysis software "NanoScope Analysis V1.40", and the surface elastic modulus E was obtained. The surface elastic modulus of the resin layer is the value measured from the surface of the resin layer in the state of the laminate, and the surface elastic modulus E of the release layer is the value measured from the surface of the release layer after the resin layer is peeled off. is.

Specifically, according to the PeakForceQNM mode manual, after configuring the cantilever warp sensitivity, spring constant, and tip curvature, measurement was performed under the following conditions, and the obtained DMT Modulus channel data was used for the resin layer and separation. It was adopted as the surface elastic modulus of the mold layer. The spring constant and the tip curvature vary depending on the individual cantilever, but the range that does not affect the measurement is a spring constant of 0.3 (N/m) or more and 0.5 (N/m) or less, and a tip curvature radius of 15 ( nm) A cantilever that satisfies the following conditions was adopted and used for measurement. Measurement conditions are shown below.
Measuring device: Burker Corporation atomic force microscope (AFM)
Measurement mode: PeakForceQNM (force curve method)
Cantilever: SCANASYST-AIR manufactured by Bruker AXS
(Material: Si, spring constant K: 0.4 (N/m), tip curvature radius R: 2 (nm))
Measurement atmosphere: 23°C, in air Measurement range: 3 (μm) Square resolution: 512 x 512
Cantilever moving speed: 10 (μm/s)
Maximum indentation load: 10 (nN).

Next, the obtained DMT Modulus channel data was analyzed with analysis software "NanoScope Analysis V1.40" and processed with Roughness. The surface elastic modulus of

[Measurement of surface free energy γ of release layer]
The surface free energy of the release layer is measured by determining the static contact angle at 25°C with water, ethylene glycol, formamide, and diiodomethane on the surface of the release layer after peeling the resin layer from the laminate. The contact angle and the dispersion term, polar term, and hydrogen bond term of the surface free energy of each liquid described in Non-Patent Document 2 are introduced into the “Hata and Kitazaki extended Hawks formula” described in Non-Patent Document 1. and obtained by solving the simultaneous equations.

The static contact angle was measured after the sample was left in an environment of 25°C for 12 hours in advance. Kyowa Interface Science Drop Master DM-501 was used, and droplets were prepared under conditions that would allow droplets to be as small as possible without creeping up the needle. The contact angle was calculated by the θ/2 method using an image taken 5 seconds after the droplet was applied to the surface of the release layer.

[Measurement of receding contact angle of 2-hydroxypropyl acrylate by expansion-shrinkage method of release layer]
Measurement of the receding contact angle of 2-hydroxypropyl acrylate by the expansion-shrinkage method of the release layer was performed using a contact angle meter Drop Master DM-501 manufactured by Kyowa Interface Science, according to the expansion-shrinkage method measurement manual of the same device. rice field.

In the measurement, a droplet of hydroxylpropyl acrylate having an initial droplet volume of 50 μL was once created on the surface of the release layer, and then the tip of the syringe needle was kept pointing to the droplet and the liquid was continuously discharged at a liquid ejection speed of 8.5 μL / s. The shape of the liquid droplet during its shrinking process was continuously photographed every 100 milliseconds, and the respective contact angles during that process were obtained.

The contact angle in the process of contraction of the droplet initially changed as the droplet contracted and then showed a constant behavior, and the contact angle at that time was taken as the receding contact angle. The method for judging that the contact angle has become constant is to line up the contact angles in the contracting direction of the droplet and select five consecutive points in that order. The average value when it became below ° was taken as the receding contact angle D ^B (°) of the measurement.

This measurement was performed 5 times for each sample, and the average value was taken as the receding contact angle of the sample. In some samples, the contact angle during the contraction process of the droplet did not become constant and continued to decrease, but the receding contact angle was set to 0°.

[Measurement of release layer by time-of-flight secondary ion mass spectrometer (TOF-SIMS)]
Using a time-of-flight secondary ion mass spectrometer TOF-SIMS 5 manufactured by ION TOF and the company's measurement software SURFACE LAB 6, the surface of the laminated film was subjected to secondary ion mass spectrometry using the following measurement conditions. T ¹ _s , T ² _s , T ¹ ₂₅ and T ² ₂₅ were obtained by measuring in the depth direction from the release layer surface.
・Measurement conditions Primary ion species: Bi ₃ ⁺⁺
Primary ion acceleration voltage: 25 kV
Pulse width: 125ns
Mass range (m/z): 0-1,000
Raster size: 50, 100 μm
Number of scans: 48, 32 Number of scanned pixels: 256 x 256.

[Characteristic evaluation of laminate]
The laminate and the resin layer were subjected to the following property evaluation, and Table 4 shows the obtained results. Unless otherwise specified, in each example and comparative example, one sample was evaluated three times at different locations, the average value was obtained, and the value was rounded off to the first decimal place.

[Evaluation of Quality of Resin Layer]
Regarding the laminates produced in Examples 1 to 12 and Comparative Examples 1 to 3, 50 m ² was visually inspected with the light source reflected on the surface of the resin layer, and deformation of 1 mm or more in diameter (repellent, foreign matter ) was observed was determined according to the following criteria. In each example and comparative example, one sample was evaluated three times at different locations, the average value was calculated, rounded off to the first decimal place, and 4 points or more were considered acceptable.
10 points: 1 or less deformations with a diameter of 1 mm or more 7 points: 2 to 3 deformations with a diameter of 1 mm or more 4 points: 4 deformations with a diameter of 1 mm or more 1 point: 5 or more deformations with a diameter of 1 mm or more.

[Peeling of resin layer, evaluation of floating]
The laminates prepared in Examples 1 to 12 and Comparative Examples 1 to 3 were cut with a cutter knife into 100 mm × 200 mm squares, and the ends of the cut parts were observed when wound around a cylinder with a diameter of 30 mm. judged accordingly. In each example and comparative example, one sample was evaluated three times at different locations, the average value was calculated, rounded off to the first decimal place, and 4 points or more were considered acceptable.
10 points: Neither the end when cut with a cutter knife nor the end when wound around a cylinder lifts.
7 points: No floatation occurs at the end when cut with a cutter knife, and slight floatation occurs at the end when wound around a cylinder.
4 points: Slight lift occurs at the end when cut with a utility knife, and slight lift occurs at the end when wound around a cylinder.
1 point: Lifting occurred at the end when cut with a utility knife, and lifting occurred at the entire end when wound around a cylinder.
0 point: no evaluable resin layer was formed.

[Evaluation of Transferability of Resin Layer to Molded Body]
On the surface of the resin layer of the laminates prepared in Examples 1 to 12 and Comparative Examples 1 to 3, one separator of an adhesive film (Panac Co., Ltd. “Panaclean” (registered trademark) PD-S1 25 μm product) was peeled off. The surfaces were laminated so as not to contain air bubbles, then the separator of the adhesive film was peeled off, and a molded body (PET film (188 μm, Toray Industries, Inc., “Lumirror” (registered trademark) T60) was laminated.

The support base material with the release layer, the release layer and the resin layer were slightly separated in advance, the support base material with the release layer was peeled off in the direction of 180 degrees, and the evaluation was made according to the following criteria. In each example and comparative example, one sample was evaluated three times at different locations, the average value was calculated, rounded off to the first decimal place, and 4 points or more were considered acceptable.
10 points: Even at a peeling speed of 10,000 mm/min, the film can be peeled uniformly within the plane.
7 points: At a peeling speed of 10,000 mm/min, the film could not be peeled uniformly, but at a speed of 1,000 mm/min, it could be peeled uniformly.
4 points: At a peeling speed of 1,000 mm/min, the film could not be peeled uniformly, but at a speed of 300 mm/min, it could be peeled uniformly.
1 point: In-plane uniform peeling is not possible at 300 mm/min.
0 point: no evaluable resin layer was formed.

1, 6, 12, 20: Laminates 2, 7, 13, 21: Support substrates with release layer 3, 8, 14, 19, 22: Support substrates 4, 9, 10, 15, 23: Release Layers 5, 11, 16, 24: Resin layer 17: Protective film 18: Adhesive layer 25: Functional layers 26, 30, 35: Release layer Surfaces 27, 31, 36: Syringe needles 28, 32, 37: Droplet 29 , 33, 38: Contact angles 34, 39: Time change of contact angles

The laminate of the present invention is excellent in scratch resistance, transportability as a thin film, and conformability to the surface shape, and also has the advantage of transferring a layer having functions such as weather resistance, gas barrier properties, and antiblocking properties. , can be suitably used for moldings such as plastics and metals.

Examples include glasses/sunglasses, cosmetic boxes, plastic molded products such as food containers, water tanks, showcases for exhibitions, etc., smartphone housings, touch panels, color filters, flat panel displays, flexible displays, flexible devices, and wearables. Devices, sensors, circuit materials, electrical and electronic applications, home appliances such as keyboards, TV/air conditioner remote controls, mirrors, window glass, buildings, dashboards, car navigation/touch panels, vehicle parts such as rearview mirrors and windows, etc. printed matter, medical film, sanitary material film, medical film, agricultural film, building material film, etc., can be suitably used for each surface material, internal material, constituent material, and manufacturing process material.

Claims (6)

A laminate having a release layer on at least one surface of a supporting substrate and a resin layer that can be peeled off from the releasing layer in this order from the supporting substrate side, wherein the resin constituting the resin layer has the chemical formula 1 and/or contains a segment having a structure of chemical formula 2, the resin constituting the release layer contains a segment having a structure of chemical formula 3 , and the surface elastic modulus of the resin layer measured by an atomic force microscope is 100 MPa or more and 2 GPa or less. and wherein the surface free energy γ (mN/m) and the surface elastic modulus E (MPa) measured by an atomic force microscope of the release layer satisfy formulas (1) and (2).
Formula 1 10≤γ≤45
Formula 2 1≤E≤1,000

where R ¹ is hydrogen or a methyl group.
R ² is any one of (i) to (vi) below.
(i) a substituted or unsubstituted alkylene group (ii) a substituted or unsubstituted arylene group (iii) a substituted alkylene group having an ether group, an ester group or an amide group inside (iv) an ether group, an ester group or Unsubstituted alkylene group having an amide group (v) A substituted arylene group having an ether group, an ester group or an amide group inside (vi) An unsubstituted arylene group ^R3 having an ether group, an ester group or an amide group inside is methyl, phenyl, vinyl or hexylene . 2. The laminate according to claim 1, wherein the release layer has an arithmetic mean roughness Ra of 5 nm or less based on JIS R1683 (2007). 3. The laminate according to claim 1, wherein the receding contact angle D ^B (°) of 2-hydroxypropyl acrylate of the release layer by an expansion-contraction method satisfies the following formula 3.
Formula 3 D ^B ≤ 40 Any one of claims 1 to 3, wherein the depth profile of the release layer measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) satisfies the following equations 4 and 5: Laminate as described.
Equation 4 T ¹ _s > T ² _s
Equation 5 T ¹ ₂₅ < T ² ₂₅
T ¹ _s : intensity of Si(CH ₃ ) ⁺ fragment ions on the release layer surface T ² _s : strongest among C _n H _2n+1 O ⁺ fragment ions (n is 1 to 3) on the release layer surface Intensity T ¹ ₂₅ of ions: Si(CH ₃ ) ⁺ fragment ion intensity T ² 25 at a depth of 25 nm from the release layer surface T 2 ₂₅ : C _n H _2n+1 O ⁺ at a depth of 25 nm from the release layer surface Intensity of the strongest fragment ion (n is 1 to 3) 5. The laminate according to any one of claims 1 to 4, wherein the resin constituting the release layer contains a segment having a structure of Chemical Formula 5.

where ^R5 is hydrogen or a methyl group.
R ⁶ is any one of (vii) to (xii) below.
(vii) a substituted or unsubstituted alkylene group (viii) a substituted or unsubstituted arylene group (ix) a substituted alkylene group having an ether group, an ester group or an amide group inside (x) an ether group, an ester group or Unsubstituted alkylene group having an amide group (xi) A substituted arylene group having an ether group, an ester group or an amide group inside (xii) An unsubstituted arylene group having an ether group, an ester group or an amide group inside 6. A method for producing a resin film, wherein the release layer and the supporting substrate are removed from the laminate according to any one of claims 1 to 5.

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