JP2011011424A - Laminated body with functional layer and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body with a functional layer which has high hardness, is excellent in abrasion resistance, followability to base material and has a laminated structure, and a molded body using the same.SOLUTION: In the laminated body 1 with the functional layer, a stress relaxation layer 3 and a surface layer 4 are laminated on at least one side surface of a resin base material 2 in this order. The surface layer 4 comprises at least silazane and an organic polymer, and the hardness H by the nanoindentation of the stress relaxation layer 3 contacting the surface layer 4 is the same as or lower than the hardness H of the surface layer 4 by the nanoindentation.

Description

  The present invention relates to a laminate with a functional layer having a novel structure and a molded body using the same.

  In recent years, in the fields of displays, touch panels, residential windows, show windows, vehicle windows, vehicle windshields, amusement machines, eyeglass lenses, etc., glass products are being replaced from the viewpoint of processability and weight reduction. Since the surface of these plastic products is basically easily damaged, a hard coat film is used for the purpose of imparting scratch resistance. In addition, with regard to conventional glass products, there are an increasing number of cases where plastic films are bonded to prevent scattering, and in order to strengthen the hardness of these film surfaces, it is widely used to form a hard coat layer on the surface. It has been broken.

  However, the conventional hard coat film has insufficient hardness of the hard coat layer, and when the underlying plastic substrate film is deformed due to the thin coating film thickness, Accordingly, the hard coat layer was also deformed, and the hardness of the hard coat film as a whole was reduced. On the other hand, in order to increase the hardness, if the thickness of the hard coat layer is increased, shrinkage of the hard coat layer occurs when the hard coat layer is formed, or if the substrate is bent, the hard coat layer breaks without following. There was a phenomenon such as. Therefore, the present situation is not particularly suitable for injection molding applications with bay bending.

  In order to increase the hardness of the hard coat layer, the resin-forming component of the hard coat layer is made of a polyfunctional acrylate ester monomer, and powdered inorganic fillers such as alumina, silica, and titanium oxide, and polymerization are started. In recent years, a method using a coating composition containing an agent, a photopolymerizable composition containing an inorganic filler composed of silica or alumina surface-treated with an alkoxysilane, and further filling with crosslinked organic fine particles have been studied. ing. Although these methods have the effect of increasing the surface hardness of the hard coat film, they have the problem of increased haze and brittle deterioration. It was not enough to meet the performance.

  Further, the hard coat layer has a two-layer structure, and fine particles of silica are added to the first layer to satisfy curling and scratch resistance. The hard coat layer has a two-layer structure, and the lower layer is a radical curable resin. A hard coat film is known in which a cured resin layer made of a blend of cationic curable resins is used and a cured resin layer made only of a radical curable resin is used as an upper layer, but these are also not sufficiently satisfactory in hardness.

  In general, it is known that increasing the thickness of the hard coat layer is effective in increasing the hardness. In particular, by increasing the thickness of the hard coat layer containing an inorganic or organic filler, the hardness of the hard coat film can be further improved, but increasing the thickness increases the haze, resulting in cracks in the hard coat layer. There are problems such that peeling easily occurs, followability to the base material is deteriorated due to curing shrinkage, and curling of the hard coat film is increased.

  For example, Patent Document 1 discloses a hard coat film for injection molding that can impart scratch resistance to the surface of an injection-molded body and has stretchability. In the method described in Patent Document 1, it is possible to increase the thickness of the hard coat layer on the base material and provide the stretchability necessary for injection molding, but it is composed of an acrylate-based hard coat layer. Therefore, it cannot be said that the performance as a hard coat layer, particularly the hardness, is sufficient. In Patent Document 2, a metal oxide fine particle having a specific blending amount on a support, three or more (meth) acryloyl groups in one molecule as an active energy ray-curable resin, and shrinkage after curing. It is composed of urethane (meth) acrylate (A) having a rate of less than 10%, polyfunctional acrylate (B) containing 3 or more (meth) acryloyl groups in one molecule, an organic solvent, and a photopolymerization initiator. A hard coat film in which a hard coat layer is formed using a coating composition is disclosed. Further, in Patent Document 3, a thermosetting property in which the hard coat layer has a volume shrinkage after curing of 2 to 10%. A hard coat film having a resin or an active energy curable resin as a main component and a thickness of the hard coat layer of 4 to 10 μm is disclosed. The hard coat films described in these patent documents are said to have improved scratch resistance, surface hardness, curl characteristics, brittleness and the like. As a result of investigation by the present inventor, the techniques disclosed in Patent Documents 2 and 3 also provide an effect of improving scratch resistance and hardness, but particularly for injection molding applications that require base material followability. It was found that the hard coat film was not satisfactory in terms of crack resistance, substrate followability (stretchability) and the like.

JP 2008-260231 A JP 2005-288787 A Japanese Patent Laid-Open No. 2005-288921

  The present invention has been made in view of the above problems, and its purpose is to provide a laminate with a functional layer having a laminated structure, which has high hardness, excellent scratch resistance and substrate followability, and molding using the same. Regarding the body, in detail, the surface of a display such as a cathode ray tube (CRT), a liquid crystal display (LCD), a plasma display panel (PDP), a field emission display (FED), a touch panel such as home appliances, various windows, for example, residential windows , Laminates with functional layers that can be used as glass protective films for show windows, vehicle windows, vehicle windshields, amusement machines, etc., protective films such as eyeglass lenses, or glass substitute resin products, and molded articles using the same There is to do.

  The above object of the present invention is achieved by the following configurations.

  1. In a laminate with a functional layer in which a stress relaxation layer and a surface layer are laminated in this order on at least one surface of a resin substrate, the surface layer is composed of at least a silazane and an organic polymer, and the stress relaxation layer in contact with the surface layer A layered product with a functional layer, wherein the hardness H by nanoindentation of the layer is equal to or lower than the hardness H by nanoindentation of the surface layer.

  2. The stress relaxation layer is composed of two or more layers having different hardness H, and the hardness H decreases from the stress relaxation layer in contact with the surface layer toward the stress relaxation layer in contact with the resin substrate. The laminated body with a functional layer as described.

  3. 2. The laminate with a functional layer according to 1 above, wherein the stress relaxation layer has a configuration in which the hardness H continuously decreases in a film thickness direction from a region in contact with the surface layer to a region in contact with the resin base material. body.

  4). 2. The stress relaxation layer is composed of two or more layers having different particle concentrations, and the particle concentration decreases from the stress relaxation layer in contact with the surface layer toward the stress relaxation layer in contact with the resin substrate. Laminated body with functional layer.

  5. 2. The laminate with a functional layer according to 1 above, wherein the stress relaxation layer has a particle concentration that continuously decreases in a film thickness direction from a region in contact with the surface layer to a region in contact with the resin base material.

  6). The stress relaxation layer has a structure in which two layers having different hardness H are alternately laminated. When the layer group having a high hardness H is an A layer unit and the layer group having a low hardness H is a B layer unit, the A layer At least one layer unit of the unit and the B layer unit is constituted by at least two layers having different dry film thicknesses, and when the A layer unit is constituted by layers having different dry film thicknesses, the A layer unit is constituted. When the dry film thickness of each layer increases toward the surface layer and the B layer unit is composed of layers having different dry film thicknesses, the dry film thickness of each layer constituting the B layer unit is 2. The laminate with a functional layer according to 1 above, wherein the total thickness ΣAh of the dry film thickness of the A layer unit decreases to the surface layer, and the total ΣBh of the dry film thickness of the B layer unit is equal. .

  7. The stress relaxation layer has a structure in which two layers having different particle concentrations are alternately laminated. When the layer group having a high particle concentration is an A layer unit and the layer group having a low particle concentration is a B layer unit, the A At least one layer unit of the layer unit and the B layer unit is composed of at least two layers having different dry film thicknesses, and when the A layer unit is composed of layers having different dry film thicknesses, When the dry film thickness of each layer constituting increases toward the surface layer and the B layer unit is composed of layers having different dry film thicknesses, the dry film thickness of each layer constituting the B layer unit is 2. The laminated layer with a functional layer according to 1 above, wherein the total thickness ΣAh of the dry film thickness of the A layer unit decreases to the surface layer and the total ΣBh of the dry film thickness of the B layer unit is equal. body.

  8). 2. The laminate with a functional layer as described in 1 above, wherein the surface layer has a silazane concentration of 50% by mass or more and 95% by mass or less.

  9. The laminate with a functional layer according to any one of 1 to 8 above, wherein the resin base material is a resin film, and loaded on one or both surfaces of the mold such that the surface layer is on the mold side. Thereafter, a molding material made of synthetic resin is injected and injected onto the laminate with a functional layer in a mold, and the laminate with the functional layer and the molding material are laminated and integrated to form. body.

  According to the present invention, the present invention has been made in view of the above problems, and the object thereof is a laminate with a functional layer having a laminated structure, which has high hardness, excellent scratch resistance and substrate followability, and the same. It was possible to provide a molded body using this.

It is sectional drawing which shows an example of the layer structure of the laminated body with a functional layer of this invention. It is sectional drawing which shows another example of the layer structure of the laminated body with a functional layer of this invention. It is sectional drawing which shows another example of the layer structure of the laminated body with a functional layer of this invention. It is a flowchart which shows an example of the production process of the lens type molded object L applicable to this invention. It is a schematic diagram which shows an example of the formation method of the molded object using the laminated body with a functional layer of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the inventor of the present invention has a functional layered laminate in which a stress relaxation layer and a surface layer are laminated in this order on at least one surface of a resin base material. A laminate with a functional layer comprising a silazane and an organic polymer, wherein the hardness H by nanoindentation of the stress relaxation layer in contact with the surface layer is equal to or lower than the hardness H by nanoindentation of the surface layer The inventors have found that a laminate with a functional layer having a laminated structure that has high hardness, excellent scratch resistance, and substrate followability can be realized, and as soon as the present invention has been achieved.

  Hereinafter, the laminated body with a functional layer of this invention and the detail of a molded object using the same are demonstrated.

<< Configuration of laminate with functional layer >>
The laminate with a functional layer of the present invention is a laminate with a functional layer in which a stress relaxation layer and a scratch-resistant surface layer are laminated in this order on at least one surface of a resin substrate, and is in contact with the surface layer. The hardness H by nanoindentation of the stress relaxation layer is equal to or lower than the hardness H by nanoindentation of the surface layer.

  The structural example which concerns on the laminated body with a functional layer of this invention is demonstrated using a figure.

  FIG. 1 is a cross-sectional view showing an example of the layer structure of the laminate with a functional layer of the present invention.

  The layer structure shown in a) of FIG. 1 shows an example of the layer structure of the laminate 1 with a functional layer defined in claim 1, and the stress relaxation layer 3, the silazane, and the organic polymer on the resin substrate 2. And a hardness H by nanoindentation of the stress relaxation layer 3 is equal to or less than the hardness H of the surface layer 4.

  When the stress relaxation layer according to the present invention has a single layer structure as shown in FIG. 1 a, the dry film thickness is preferably 1.0 to 30 μm, and the hardness H is 0. It is preferably 1 to 1.0 GPa.

  In addition, the hardness H as used in the field of this invention is the hardness measured by nanoindentation.

  In the nanoindentation method, a sample is continuously loaded and unloaded with a very small load, and the hardness (Hardness, hereinafter abbreviated as H) is measured from the obtained load-displacement curve. Is the method.

  The hardness (H) of nanoindentation represents the value of the direct surface hardness of the sample. Therefore, the hardness (H) of nanoindentation is suitable as an index of surface hardness.

<Measurement of hardness (H) by nanoindentation method>
The measurement of hardness (H) by the nanoindentation method of the present invention was performed by attaching a sample to a Triscope from Hysitron and a Nanoscope III from Digital Instruments. For the measurement, a triangular pyramid diamond indenter called a Belkovic indenter (tip ridge angle 142.3 °) is used as an indenter.

  A triangular pyramid-shaped diamond indenter was applied to the sample surface at a right angle, a load was gradually applied, and the load was gradually returned to 0 after reaching the maximum load. The value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion was calculated as the hardness (H). The maximum load condition at this time is 100 μN. Details regarding the principle of surface hardness measurement by the nanoindentation method are described in, for example, Handbook of Micro / Nano Tribology (CRC edited by Bharat Bhushan).

  The layer configuration shown in FIG. 1 b shows an example of the layer configuration of the laminate 1 with a functional layer defined in claim 2, and the stress of two or more layers having different hardness H on the resin substrate 2. In the relaxation layer (b in FIG. 1, a two-layer structure is shown as an example) and a surface layer 4 containing silazane and an organic polymer is laminated, and the stress relaxation layer composed of two or more layers is a surface layer. 4 from the stress relaxation layer 3-2 in the stress relaxation layer in contact with 4 (b in FIG. 1) to the stress relaxation layer 3-1 in the stress relaxation layer in contact with the resin substrate 2 (b in FIG. 1). It is preferable to adopt a configuration that lowers.

  In the layer structure shown in FIG. 1 b), as the two or more stress relaxation layers having different hardness H, the dry film thickness is preferably 1.0 to 30 μm, and the stress relaxation layer having high hardness H. The hardness is preferably 0.3 to 3.0 GPa, the hardness of the stress relaxation layer having a low hardness H is preferably 0.1 to 1.0 GPa, and the hardness H difference between the stress relaxation layers Is preferably 0.1 to 0.5 GPa.

  The layer configuration shown in c) of FIG. 1 shows an example of the layer configuration of the laminate 1 with a functional layer defined in claim 3, and the stress relaxation layer 3, the silazane, and the organic polymer on the resin substrate 2. And the stress relaxation layer 3 has a configuration in which the hardness H continuously decreases in the film thickness direction from the region B in contact with the surface layer 4 toward the region A in contact with the resin base material 2. It is characterized by. The hardness H in the region B of the stress relaxation layer 3 in contact with the surface layer 4 referred to in the present invention is the hardness H measured on the surface of the stress relaxation layer 3 in contact with the surface layer 4. Hardness H of the surface of the stress relaxation layer in contact with.

  In the layer configuration shown in FIG. 1 c), the hardness H in the region B is preferably 0.3 to 3.0 GPa, and the hardness H in the region A is 0.1 to 1.0 GPa. It is preferable.

  The layer structure shown in d) of FIG. 1 shows an example of the layer structure of the laminate 1 with a functional layer defined in claim 4, and two or more layers having different particle concentrations are formed on the resin substrate 2. In the stress relaxation layers 3-i and 3-b (shown in FIG. 1d), a two-layer structure is shown as an example, and a surface layer 4 containing silazane and an organic polymer is laminated to have two or more layers. The stress relaxation layer is composed of the stress relaxation layer 3 in the stress relaxation layer (d in FIG. 1) in contact with the resin substrate 2 from the stress relaxation layer 3-b in the stress relaxation layer in contact with the surface layer 4 (d in FIG. 1). -It is preferable to make it the structure which particle concentration becomes low toward (b).

  In the layer structure shown in FIG. 1 d), the stress relaxation layer having two or more layers having different particle concentrations preferably has a dry film thickness of 1.0 to 30 μm, and has a high particle concentration. The particle concentration is preferably 30 to 70% by volume, the particle concentration of the stress relaxation layer having a low particle concentration is preferably 0 to 40% by volume, and the particle concentration difference between the stress relaxation layers is It is preferable that it is 5.0-20 volume%.

  The particle concentration in the stress relaxation layer referred to in the present invention is determined by measuring the particle filling rate (volume%). That is, it is usually determined as the ratio of particles (solid content volume ratio) to the solid content (components other than the solvent) in the stress relaxation layer coating solution for forming the stress relaxation layer. In the case of using a curable resin, the active energy ray curable resin contracts simultaneously with curing due to a reaction by irradiation with an active energy ray, and thus was determined by a filling rate measurement method shown below.

<Filling rate measurement method (volume analysis method)>
The filling rate of particles in the film after drying was measured by the following method. After applying the stress relaxation layer coating solution onto the resin substrate by a wet coating method to form the stress relaxation layer, the stress relaxation layer is peeled off from the resin substrate, and the total volume is measured. The volume of the particles contained by dissolution was measured, and the particle filling rate (volume%) was determined from the measured values.

  The layer structure shown in e) of FIG. 1 shows an example of the layer structure of the laminate 1 with a functional layer defined in claim 5, and the stress relaxation layer 3, the silazane, and the organic polymer on the resin substrate 2. And the stress relaxation layer 3 has a structure in which the particle concentration continuously decreases in the film thickness direction from the region B in contact with the surface layer 4 toward the region A in contact with the resin base material 2. It is characterized by. According to the present invention, whether the particle concentration is continuously different or not is determined by a method for measuring the filling rate at an arbitrary position by the filling rate measuring method described above, or as a simple method, stress relaxation. The cross section of the layer 3 can be observed with an electron microscope or the like to determine whether or not the particle density is continuously changing.

  In the layer configuration shown in e) of FIG. 1, the particle concentration in the region B is preferably 30 to 70% by volume, and the particle concentration in the region A is preferably 0 to 40% by volume.

  Moreover, in the laminated body with a functional layer of the present invention, the stress relaxation layer has a structure in which two layers having different hardness H are alternately laminated. A layer group having a high hardness H is an A layer unit, and the hardness H is low. When the layer group is a B layer unit, at least one layer unit of the A layer unit and the B layer unit is composed of at least two layers having different dry film thicknesses, and the A layer unit is a layer having different dry film thicknesses. When configured, the dry film thickness of each layer constituting the A layer unit increases from the resin base toward the surface layer, and the B layer unit is composed of layers having different dry film thicknesses. The dry film thickness of each layer constituting the B layer unit decreases from the resin substrate toward the surface layer, and the total dry film thickness ΣAh of the A layer unit and the dry film thickness of the B layer unit A configuration in which ΣBh is equivalent is preferable.

  That is, as shown in FIG. 2 a), in the A layer unit, which is a layer group having a relatively high hardness H, the dry film thicknesses in the order of 3A-1 and 3A-2 toward the surface layer 4. In the B layer unit, which is a layer group having a relatively low hardness H, the dry film thickness decreases in the order of 3B-1 and 3B-2 toward the surface layer 4. . In addition, the sum ΣAh of the dry film thicknesses of 3A-1 and 3A-2 constituting the A layer unit and the sum ΣBh of the dry film thicknesses of 3B-1 and 3B-2 constituting the B layer unit should be equal. Is a preferred embodiment. The sum ΣAh of the dry film thickness of the A layer unit in the present invention is equivalent to the sum ΣBh of the dry film thickness of the B layer unit. That is, the difference in the sum of the dry film thicknesses of both is within 10%. Said, preferably within 5%.

  In the layer configuration shown in FIG. 2 a), the hardness H of the A layer unit is preferably 0.3 to 3.0 GPa, and the hardness H of the B layer unit is 0.1 to 1. It is preferably 0 GPa. Moreover, it is preferable that it is 1.0-20 micrometers as the sum total of the dry film thickness of each of A layer unit and B layer unit.

  In the laminate with a functional layer of the present invention, the stress relaxation layer has a structure in which two layers having different particle concentrations are alternately laminated. A layer group having a high particle concentration is represented by an A layer unit, and the particle concentration is When the lower layer group is a B layer unit, at least one layer unit of the A layer unit and the B layer unit is composed of at least two layers having different dry film thicknesses, and the A layer unit is a layer having different dry film thicknesses. When the dry layer thickness of each layer constituting the A layer unit increases from the resin base toward the surface layer, and the B layer unit is composed of layers having different dry thicknesses The dry film thickness of each layer constituting the B layer unit decreases from the resin base toward the surface layer, and the total dry film thickness ΣAh of the A layer unit and the dry film thickness of the B layer unit The total sum ΣBh is preferably equal.

  That is, as shown in FIG. 2 b), for example, in the A layer unit, which is a layer group having a relatively high particle concentration, the dry film thicknesses in the order of 3A-I, 3A-B toward the surface layer 4. In contrast, in the B layer unit, which is a group of layers having a relatively low particle concentration, the dry film thickness decreases in the order of 3B-I and 3B-B toward the surface layer 4. . In addition, the sum ΣAh of the dry film thicknesses of 3A-A and 3A-B constituting the A layer unit and the sum ΣBh of the dry film thicknesses of 3B-I and 3B-B constituting the B layer unit should be equal. Is a preferred embodiment. The sum ΣAh of the dry film thickness of the A layer unit in the present invention is equivalent to the sum ΣBh of the dry film thickness of the B layer unit. That is, the difference in the sum of the dry film thicknesses of both is within 10%. Said, preferably within 5%.

  In the layer configuration shown in FIG. 2 b), the particle concentration of the A layer unit is preferably 30 to 70% by volume, and the particle concentration of the B layer unit is 0 to 40% by volume. Is preferred. Moreover, it is preferable that it is 1.0-20 micrometers as the sum total of the dry film thickness of each of A layer unit and B layer unit.

  Subsequently, the detail of each component of the laminated body with a functional layer of this invention is demonstrated.

<Surface>
The surface layer according to the present invention is composed of at least silazane and an organic polymer.

  First, silazane applicable to the present invention will be described.

  The silazane applicable to the present invention is not particularly limited, but is preferably polysilazane, and further has a number average molecular weight of 100 to 5 having a main skeleton composed of units represented by the following general formula (I). The polysilazane is preferred.

Formula (I)
-(Si (R ¹ ) (R ² ) -N (R ³ )) _n-
In the general formula (I), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group directly connected to silicon other than these groups is carbon. It represents a certain group, an alkylsilyl group, an alkylamino group, or an alkoxy group. However, at least one of R ¹ , R ² , and R ³ is a hydrogen atom. n is an integer having a molecular weight of 100 to 50,000.

In the present invention, the polysilazane is preferably a polysilazane having at least a Si—H bond or an N—H bond in the molecule. In particular, in the general formula (I), R ¹ , R ² , R ³ Inorganic polysilazane (perhydropolysilazane) in which all or most are hydrogen atoms, for example, see JP-B-63-16325, JP-A-1-138108, JP-A-1-138107, JP-A-4-63833, or the like Polysilazane, for example, random copolymer silazane described in JP-A-3-31326, polysiloxazan described in JP-A-62-195024, polymetallosilazane described in JP-A-2-77427, and the like, are preferred. In addition to polysilazane and other polymers, and polysilazane and other polymers It is a mixture of mono-, polysilazane, particularly the characteristics of the inorganic polysilazane available unless lost.

  Polysilazanes applicable to the surface layer according to the present invention include those having a chain, cyclic or cross-linked structure, or those having a plurality of these structures in the molecule, and these can be used alone or in a mixture. Typical examples of polysilazane used include the following, but are not limited thereto.

In the general formula (I), R ¹ , R ² and R ³ having a hydrogen atom is perhydropolysilazane, and the production method thereof is described in, for example, Japanese Patent Publication No. 63-16325, D.C. Seyferth et al. Communication of Am. Cer. Soc. , C-13, January 1983. Has been reported.

In the above general formula (I), a method for producing a polysilazane having a hydrogen atom in R ¹ and R ² and a methyl group in R ³ is described in D.C. See Seyferth et al., Polym. Prepr. , Am. Chem. Soc. , Div. Polym. Chem. 25, 10 (1984). The polysilazane obtained by this method is a chain polymer having a repeating unit of — (SiH ₂ NCH ₃ ) — and a cyclic polymer, and neither has a crosslinked structure.

In the above general formula (I), a method for producing a polyorgano (hydro) silazane having a hydrogen atom in R ¹ and R ³ and an organic group in R ² is described in D.C. See Seyferth et al., Polym. Prepr. , Am. Chem. Soc. , Div. Polym. Chem. 25, 10 (1984) and JP-A-61-89230. The polysilazanes obtained by these methods include those having a cyclic structure with a polymerization degree of 3 to 5 mainly having — (R ² SiHNH) — as the repeating unit, and (R ³ SiHNH) X [(R ₂ SiH) _{1. 5} N] _1-X (0.4 <x <1) Some molecules have a chain structure and a cyclic structure in the molecule.

In the general formula (I), a hydrogen atom in ^{R 1,} polysilazane having an organic group in ^{R 2} and ^{R 3,} also organic radicals ^{R 1} and ^{R 2,} those having a hydrogen atom in ^{R 3} - ^(R 1 ^{R 2} It has a cyclic structure mainly having a degree of polymerization of 3 to 5, using SiNR ³ )-as a repeating unit. The polysilazane used has a main skeleton composed of the units represented by the general formula (I) as described above, but the units represented by the general formula (I) may be cyclized as is apparent from the above. In the case where the cyclic portion is a terminal group, and when such a cyclization is not performed, the terminal of the main skeleton can be the same group as R ¹ , R ² , R ³ or hydrogen.

  Some polyorgano (hydro) silazanes include D.I. Seyferth et al. Communication of Am. Cer. Soc. , C-132, July 1984. Some have a cross-linked structure in the molecule as reported.

Other polysilazanes applicable to the present invention include repeating units [(SiH ₂ ) _n (NH) _m ] and [(SiH ₂ ) _r O] as reported in JP-A-62-195024. (In these formulas, n, m and r are 1, 2 or 3, respectively) produced by reacting a boron compound with a polysiloxazan represented by polysilazane as reported in JP-A-2-84437. Polyborosilazane having excellent heat resistance, polymetallo produced by reacting polysilazane and metal alkoxide as reported in JP-A-63-81122, JP-A-63-191832 and JP-A-2-77427 Silazane, JP-A-1-138108, 1-138107, 1-203429, 1-203430, 4-63833, 3- The molecular weight as reported in 320167 was increased (the former four of the above publication), and the hydrolysis resistance was improved (the latter two), inorganic silazane high polymers and modified polysilazanes, No. 175726, No. 5-86200, No. 5-331293, No. 3-31326, a copolymer silazane advantageous for thickening by introducing an organic component into polysilazane, and JP-A-5-238827 Catalytic compounds for promoting ceramicization of polysilazane as reported in JP-A-4-272020, JP-A-5-93275, JP-A-5-214268, JP-A-5-30750 and JP-A-5-338524 It can be applied to metals such as plastics and aluminum with or without adding low temperature hardening polysilazane, etc. It can be used as.

  When polysilazane is mixed with acrylic resin particles, polysilazane is usually dissolved in a solvent. Solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbon hydrocarbon solvents, halogenated hydrocarbons such as halogenated methane, halogenated ethane, and halogenated benzene, aliphatic ethers, and alicyclic ethers. Etc. can be used. Preferred solvents are halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, ethylidene chloride, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-dioxyethane, dioxane. , Ethers such as dimethyldioxane, tetrahydrofuran, tetrahydropyran, cellosolve acetate, carbitol acetate, pentanehexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, And hydrocarbons such as toluene, xylene, and ethylbenzene.

  The surface layer according to the present invention is characterized by containing an organic polymer together with silazane. Examples of the organic polymer applicable to the present invention include (meth) acrylic, (meth) acrylic-styrene, styrene, Polymers such as styrene-butadiene organic polymers can be mentioned, and among them, acrylic polymers are particularly preferable.

  As the acrylic polymer applicable to the present invention, various polymers can be used. For example, acrylic acid ester (as alcohol residue, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group and the like); methacrylate ester (alcohol residue is the same as above); 2-hydroxyethyl acrylate, Hydroxy-containing monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-methylol acrylamide, N- Amide group-containing monomers such as tyrolmethacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-phenylacrylamide, etc .; N, N-diethylaminoethyl acrylate, N, N-diethylamino Amino group-containing monomers such as ethyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether; styrene sulfonic acid, vinyl sulfonic acid, and salts thereof (for example, sodium salt, potassium salt, ammonium salt, etc.) Monomers containing a sulfonic acid group or a salt thereof such as crotonic acid, itaconic acid, acrylic acid, maleic acid, fumaric acid, and salts thereof (for example, sodium salt, potash) Monomers containing a carboxyl group such as a salt or ammonium salt) or a salt thereof; monomers containing an anhydride such as maleic anhydride or itaconic anhydride; other vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl Made from a combination of ethers, vinyltrisalkoxysilanes, alkylmaleic acid monoesters, alkyl fumaric acid monoesters, acrylonitrile, methacrylonitrile, alkylitaconic acid monoesters, vinylidene chloride, vinyl acetate, vinyl chloride, etc. However, those containing 50 mol% or more of a (meth) acrylic monomer component such as an acrylic acid derivative or a methacrylic acid derivative are preferred, and those containing a methyl methacrylate component are particularly preferred. . In addition, an acrylic polymer containing fluorine, such as poly (perfluoro-t-butyl methacrylate), poly (perfluoroisopropyl methacrylate), poly (hexafluoro-2-propyl methacrylate), poly (trifluoroethyl methacrylate), (meth) acrylic acid, Fluorinated ester polymers have the advantage of excellent sliding properties and water repellency. In the present invention, a polysilazane and an acrylic polymer are compatible with each other, and if an appropriate acrylic polymer is selected, a stable coating solution can be obtained without degrading the polysilazane. Thus, it is possible to obtain a coating that complements the disadvantages of both. Solvents that can dissolve acrylic polymers include esters such as ethyl acetate and n-butyl acetate, glycol ethers such as cellosolve and cellosolve acetate, hydrogenated flames such as toluene and xylene, and ketones such as acetone and methyl ethyl ketone. Can be mentioned.

  When preparing a coating solution for forming a surface layer containing polysilazane and an acrylic polymer, generally a solution of polysilazane and an acrylic polymer solution may be mixed. The blending amount of the polysilazane and the acrylic polymer can be widely selected according to the application of the coating. For example, when flexibility is important, the total solid content [total amount of the polysilazane and the acrylic polymer] is 100% by mass. The polysilazane is in the range of 3 to 30% by mass, and in the case of emphasizing hardness and heat resistance, it is preferably in the range of 30 to 97% by mass. In the surface layer according to the present invention, in particular, the silazane concentration is It is preferable that they are 50 mass% or more and 95 mass% or less.

  In the preparation of the coating solution for forming the surface layer according to the present invention, the solvent that dissolves polysilazane and acrylic resin is preferably a solvent that stably dissolves both polysilazane and acrylic resin. For example, xylene, toluene, butylcarbyl Tall acetate, n-butyl acetate and the like are preferable. When a solvent is used, two or more kinds of solvents may be mixed in order to adjust the solubility of the acrylic resin-added polysilazane and the evaporation rate of the solvent.

  In the present invention, an appropriate filler may be added as necessary. Examples of the filler include fine oxides of oxide inorganic substances such as silica, alumina, zirconia and mica, or non-oxide inorganic substances such as silicon carbide and silicon nitride. Depending on the application, metal powders such as aluminum, zinc and copper can be added. In more detail, examples of fillers include silica sand, quartz, novaculite, diatomaceous earth, etc .: synthetic amorphous silica: kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, aluminum silicate Silicates such as: glass powder, glass spheres, hollow glass spheres, glass flakes, foam glass spheres and other glass bodies: boron nitride, boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, nitriding Non-oxide inorganic materials such as titanium and titanium carbide: Calcium carbonate: Metal oxides such as zinc oxide, alumina, magnesia, titanium oxide, and beryllium oxide: Barium sulfate, molybdenum disulfide, tungsten disulfide, carbon fluoride and other inorganic materials: Metal powder such as aluminum, bronze, lead, stainless steel, zinc: carbon Black, coke, graphite, pyrolytic carbon, carbon and the like of the hollow carbon spheres and the like.

  In the coating liquid composition for forming a surface layer according to the present invention, various pigments, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusting agents, dispersing agents, surface modifiers, plasticizers are necessary. Drying accelerators and flow inhibitors may be added.

  The surface layer according to the present invention is a surface layer forming coating solution, for example, spin coating, brush coating, spraying (spraying), dip coating, blade coating, roll coating, ink jet printing, gravure printing, screen printing. , Flexographic printing, bar coating method, die coating method and the like. Above all, in the case of automotive applications, spraying methods such as air spray and airless spray, methods using rotary atomizing coating machines, electrostatic coating machines, etc .; when applying to plastic films, gravure printing, flexographic printing, etc. The printing method, dip coating method, blade coating method, roll coating method, bar coating method and the like are preferable. In applying the coating agent, an undercoat layer may be provided on the article to be coated from the viewpoint of adhesion or the like. Moreover, when the coating agent of this invention uses a solvent, it is preferable to dry on the said conditions after the said application | coating.

  Although the thickness of a surface layer changes with uses and is not specifically limited, For example, 3-100 micrometers is preferable, More preferably, it is 5-40 micrometers. Among these, 10 to 100 μm is preferable for automobile applications, and 3 to 50 μm is preferable for top coats for plastic films. When the surface layer is thinner than the above preferred range, the scratch resistance may be reduced, and when it is thick, the cost may be disadvantageous, and the design property may be reduced, or the surface layer itself may be easily peeled off.

《Stress relaxation layer》
(Constituent materials)
Each layer constituting the stress relaxation layer or the A layer unit and the B layer unit according to the present invention is mainly formed with a configuration containing an actinic ray curable resin and, if necessary, particles, preferably inorganic particles.

<Actinic ray curable resin>
Typical examples of the actinic ray curable resin applicable to the present invention include an active energy ray curable resin and an electron beam curable resin, but even a resin that is cured by irradiation with actinic rays other than ultraviolet rays and electron beams. Good. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.

  In general, UV-curable acrylic urethane-based resins are obtained by further reacting 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate, methacrylate) with a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, see JP-A-59-151110).

  The UV curable polyester acrylate resin can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer (see, for example, JP-A-59-151112). .

  Specific examples of the ultraviolet curable epoxy acrylate resin include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoinitiator added thereto (for example, JP-A-1- No. 105738). As the photoreaction initiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.

  Specific examples of ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate. Etc. can be mentioned.

  These resins are usually used together with known photosensitizers. Moreover, the said photoinitiator can also be used as a photosensitizer. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. Further, when using an epoxy acrylate photoreactant, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying can be added in an amount of usually 1 to 10% by mass of the composition, and 2.5 to 6 It is preferable that it is mass%.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  For example, as an ultraviolet curable resin, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo Co., Ltd.) Or Koei hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), or Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP- 10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above Manufactured by Dainichi Seika Kogyo Co., Ltd.), or KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB Corporation), or RC-5015, RC-5016, RC-5020, RC-5031, RC -5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.) or Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), or Sun Rad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), or RCC-15C (Grace Japan Co., Ltd.) (Manufactured by company), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available ones.

<Inorganic particles>
In the stress relaxation layer according to the present invention, it is preferable to contain particles, more preferably to contain inorganic particles. Examples of inorganic particles applicable to the constituent layers of the stress relaxation layer according to the present invention include Si, Metal oxide fine particles selected from Ti, Mg, Ca, Zr, Sn, Sb, As, Zn, Nb, In, and Al are preferable. Specifically, silicon oxide, titanium oxide, aluminum oxide, tin oxide , Indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate be able to. In particular, in the present invention, it is preferable to use silicon oxide as the inorganic particles.

  As silicon oxide that can be preferably applied to the present invention, for example, preferably used silicon oxide particles are: Silicia manufactured by Fuji Silysia Chemical Co., Ltd., Nippon Sil E manufactured by Nippon Silica Co., Ltd., manufactured by Nippon Aerosil Co., Ltd. Aerosil series, colloidal silica manufactured by Nissan Chemical Industries, organosilica sol, etc. can be applied.

  The average particle diameter of the inorganic particles applicable to the stress relaxation layer according to the present invention is preferably 5 nm or more and 1.0 μm or less, and more preferably 5 nm or more and 500 nm or less. The average particle diameter of the inorganic particles is obtained as a simple average value (number average) by observing the inorganic particles with an electron microscope, determining the particle diameter of 100 arbitrary primary particles. Here, each particle diameter is expressed by a diameter assuming a circle equal to the projected area.

  In the stress relaxation layer according to the present invention, the content of the inorganic particles in the stress relaxation layer is not particularly limited as long as it satisfies the conditions defined in the present invention.

  In addition to the constituent materials described above, various additives can be used in the stress relaxation layer according to the present invention as long as the object effects of the present invention are not impaired. When preparing the stress relaxation layer coating solution, an organic solvent can be used. For example, hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, Methyl ethyl ketone, methyl isobutyl ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents can be appropriately selected or used by mixing them. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It can be contained by mass%.

  When preparing the stress relaxation layer coating liquid, it is preferable to add a silicon compound. For example, polyether-modified silicone oil is preferably added.

  In order to increase the heat resistance of the stress relaxation layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

  Further, the stress relaxation layer preferably contains a silicon surfactant or a polyoxyether compound. Polyether-modified silicon is preferable as the silicon-based surfactant, and specifically, BYK-UV3500, BYK-UV3510, BYK-333, BYK-331, BYK-337 (manufactured by BYK-Chemical Japan), TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicon), KF-351, KF-351A, KF-352, KF-353, KF-354, KF-355, KF-615, KF-618, KF-945, KF- 6004 (polyether-modified silicone oil; manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are exemplified, but not limited thereto.

  The stress relaxation layer may contain a fluorine-siloxane graft polymer. The fluorine-siloxane graft polymer refers to a copolymer polymer obtained by grafting polysiloxane containing siloxane and / or organosiloxane alone and / or organopolysiloxane to at least a fluorine-based resin.

<Method for forming stress relaxation layer>
In the present invention, as a method for forming the stress relaxation layer according to the present invention on a resin substrate or the like, a known method for forming a thin film can be applied, and in particular, a wet coating method is used. Is preferred.

  The wet coating method is, for example, an actinic ray curable resin dissolved in a solvent, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, and then inorganic particles are added to the inorganic particles. For preparing a layer coating solution containing no or an inorganic particle obtained by dissolving an actinic radiation curable resin in a solvent, and forming a wet thin film on a resin substrate using the coating solution It is.

  Examples of coating methods used in such wet coating methods include spin coating, dip coating, extrusion coating, roll coating coating spray coating, gravure coating, wire bar coating, air knife coating, slide popper coating, and curtain coating. A coating method (coating apparatus) using a known solution can be applied.

The stress relieving layer (stress relieving layer) formed on the resin substrate by the above application method is irradiated with actinic rays for the purpose of curing the film. As a light source for forming a cured film layer by a photo-curing reaction of an actinic ray curable resin, any light source that generates ultraviolet rays can be used. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, A high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, etc. can be mentioned. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. It can be used by using a sensitizer having an absorption maximum in the near ultraviolet region to the visible light region.

  The UV curable resin composition is applied and dried, and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 from the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.

  When the layer constituting the A layer unit and the layer constituting the B layer unit according to the present invention are alternately laminated, the first layer is coated on the resin substrate by a wet coating method. Then, after irradiating actinic rays, a second layer is applied on the first layer, and then actinic rays are irradiated.

  When forming a stress relaxation layer in which hardness or particle concentration changes continuously in a single layer, for example, a coater capable of simultaneous multi-layer coating with wet on wet, such as a slide hopper type coater or Using a curtain coater, a plurality of stress relaxation layer coating liquids having different particle concentrations are used. For example, the lowermost layer uses a stress relaxation layer coating liquid having the lowest particle concentration, and the coating liquid increases in particle concentration as it becomes an upper layer sequentially. As a constitution, it is obtained by applying simultaneous multilayer coating on a resin substrate, allowing a certain amount of time to pass, mixing some layers between the interfaces, and then curing by irradiating with ultraviolet light from a light source. be able to.

  As a coating apparatus applicable to the multilayer simultaneous coating method, a supply port or a supply slit capable of supplying a plurality of coating liquids is provided, and the supply amount of the coating liquid to each supply port or the supply slit so as to obtain a desired dry film thickness For example, a coating device such as extrusion coating, slide hopper coating, curtain coating, or the like can be applied.

<Resin substrate>
The resin base material constituting the laminate with a functional layer of the present invention is not particularly limited, but is a polyolefin (PO) resin such as a homopolymer or copolymer such as ethylene, propylene, or butene, or a cyclic polyolefin. Polyester resins such as amorphous polyolefin resin (APO), polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), polyamide (PA) resin such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, polyvinyl alcohol resin such as ethylene-vinyl alcohol copolymer (EVOH), polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin , Polyetheretherketone (PEEK) resin Polycarbonate (PC) resin, acrylic resin, polystyrene resin, vinyl chloride resin, polyvinyl butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride ( PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoroethylene-perfluoropropylene-perfluorovinyl ether copolymer (EPA) ) And the like can be used.

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof.

  The resin bases exemplified above can be obtained as commercial products, such as ZEONEX and ZEONOR (manufactured by ZEON Corporation), amorphous cyclopolyolefin resin film ARTON (manufactured by GS Corporation), polycarbonate, and the like. Examples include a pure ace film (manufactured by Teijin Ltd.) and a cellulose triacetate film Konica Katak KC4UX, KC8UX (manufactured by Konica Minolta Opto Co., Ltd.).

  Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, as a resin film base material.

  The resin substrate according to the present invention may be in the form of a sheet, a film, or other forms, and the form is not particularly limited. The film thickness of the resin base material can be appropriately selected from a wide range according to various conditions such as the type of resin to be used and the intended use, but is usually in the range of 10 μm to 10 mm, preferably 100 μm to 5 mm.

<Production of molded body>
The molded body of the present invention is a laminate with a functional layer of the present invention in which the resin base material is a resin film. After the surface layer is on the mold side, the laminate is loaded on one or both surfaces of the mold. A molding material made of a synthetic resin is injected and injected onto the laminate with a functional layer in a mold, and the laminate with a functional layer and the molding material are laminated and integrated.

  FIG. 3 is a schematic diagram showing an example of a method for forming a molded body using the laminate with a functional layer of the present invention. As a specific method, as shown in FIG. This is a method of forming the molded body 7 by adhering the laminate 1 with a functional layer in which the stress relaxation layer 3 and the surface layer 4 are laminated on the resin substrate B so that the surface layer 4 becomes the surface.

  Next, a more specific method of forming the molded body of the present invention will be described with reference to the drawings.

  FIG. 4 is a flowchart showing a manufacturing process of the lens mold body L1.

  As shown to a) of FIG. 4, the laminated body 1 with a functional layer is fixed with the clamp 201 so that a surface layer may become upper. Next, as shown in FIG. 4 b, the laminate with functional layer 1 is drawn down (the functional layer due to its own weight during heating) using the heaters 203 disposed above and below the laminate with functional layer 1. “Sag” of the laminate. Next, as shown in FIG. 4 c), the functional layer-equipped laminate 1 and the lens mold 202 are brought into contact from below the functional layer-equipped laminate 1. Next, as shown in FIG. 4 d), the lower layer of the lens mold 202 is depressurized in the X direction to bring the functional layered laminate 1 and the lens mold 202 into close contact with each other. Next, as shown in e) of FIG. 4, after cooling and solidifying the laminate 1 with a functional layer, the lens mold 202 is released, the clamp 201 is removed, and as shown in f) of FIG. Then, extra portions that were not molded were trimmed to obtain lens-shaped molded bodies L1 (lens-type laminate with functional layer 1) having a surface layer on the convex surface side.

  FIG. 5 is a schematic diagram showing an example of a method for forming a lens mold molded body.

  In FIG. 5, a lens mold molded body L <b> 1 (laminated body 1 with a lens mold functional layer) produced by the method shown in FIG. 4 is placed in the first injection mold 10 and the surface layer 4 faces the first injection mold 10. After placing the second injection mold 9, the polycarbonate resin 12 is injected into the cavity from the injection port 11 at a resin temperature of 300 ° C., a mold temperature of 90 ° C., and an injection pressure of 10 MPa. This is a method for obtaining a convex lens-like lens mold molded body L provided with the functional layer laminated body 1 on the surface of the resin 12.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Preparation of coating solution for surface layer >>
(Preparation of surface layer coating solution 1)
Polysilazane: NAX120-20 (manufactured by AZ Electronic Materials)
3.48g
Acrylic resin: BR101-20DB (manufactured by AZ Electronic Materials)
1.52g
Dibutyl ether (manufactured by AZ Electronic Materials) 5.00g
The above additives were sequentially mixed and stirred for 30 minutes to obtain a surface layer coating solution 1 containing 70% by mass of polysilazane in a solid content ratio.

  The surface hardness of the surface layer 1 at a dry film thickness of 1.0 μm formed by the surface layer coating solution 1 measured by the method described later was 2.1 GPa.

(Preparation of surface layer coating solution 2)
Polysilazane: NAX120-20 (manufactured by AZ Electronic Materials)
4.00 g
Acrylic resin: BR101-20DB (manufactured by AZ Electronic Materials)
1.00g
Dibutyl ether (manufactured by AZ Electronic Materials) 5.00g
The above additives were sequentially mixed and stirred for 30 minutes to obtain a surface layer coating solution 2 containing 80% by mass of polysilazane in a solid content ratio.

  The surface hardness of the surface layer 2 at a dry film thickness of 1.0 μm formed by the surface layer coating solution 2 measured by the method described later was 2.4 GPa.

(Preparation of surface layer coating solution 3)
Polysilazane: NAX120-20 (manufactured by AZ Electronic Materials)
5.00g
Dibutyl ether (manufactured by AZ Electronic Materials) 5.00g
The above additives were sequentially mixed and stirred for 30 minutes to obtain a surface layer coating solution 3 containing 100% by mass of polysilazane in a solid content ratio.

  The surface hardness of the surface layer 3 at a dry film thickness of 1.0 μm formed by the surface layer coating solution 3 measured by the method described later was 3.0 GPa.

(Preparation of surface layer coating solution 4)
Polysilazane: NAX120-20 (manufactured by AZ Electronic Materials)
1.25g
Acrylic resin: BR101-20DB (manufactured by AZ Electronic Materials)
3.75g
Dibutyl ether (manufactured by AZ Electronic Materials) 5.00g
The above additives were sequentially mixed and stirred for 30 minutes to obtain a surface layer coating solution 4 containing 25% by mass of polysilazane in a solid content ratio.

  The surface hardness of the surface layer 4 at a dry film thickness of 1.0 μm formed by the surface layer coating solution 4 measured by the method described later was 0.8 GPa.

<< Preparation of coating solution for stress relaxation layer >>
(Preparation of coating solution 1 for stress relaxation layer)
UV curable resin: Beam set 575CB, urethane acrylate resin, Arakawa Chemical Industries, Ltd. 10.97g
Photoinitiator: Irgacure 184, Ciba Japan Co., Ltd. 0.55 g
Methyl ethyl ketone 24.03g
The above additives were sequentially mixed and stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1.0 μm to prepare a stress relaxation layer coating solution 1.

(Preparation of coating solution 2 for stress relaxation layer)
UV curable resin: B-1405, acrylate resin, manufactured by Shin-Nakamura Scientific Co., Ltd.
13.25g
Photoinitiator: Irgacure 184, Ciba Japan 0.66g
Methyl ethyl ketone 21.75g
The above additives were sequentially mixed and stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1.0 μm to prepare a stress relaxation layer coating solution 2.

(Preparation of coating solution 3 for stress relaxation layer)
UV curable resin: Beamset 575CB, urethane acrylate resin, 5.02 g made by Arakawa Chemical Industries, Ltd.
Photoinitiator: Irgacure 184, Ciba Japan 0.25g
Inorganic particle dispersion: containing 30% by mass of silicon oxide, methyl ethyl ketone-dispersed silica sol (manufactured by Nissan Chemical Co., Ltd., trade name IPA-ST-ZL), average primary particle size of silicon oxide particles = 100 nm
30.45g
Methyl ethyl ketone 0.52g
The above additives were sequentially mixed and stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1.0 μm to prepare a stress relaxation layer coating solution 3.

(Preparation of coating solution 4 for stress relaxation layer)
UV curable resin: Beam set 575CB, urethane acrylate resin, 21.2 g made by Arakawa Chemical Industries, Ltd.
Photoinitiator: Irgacure 184, manufactured by Ciba Japan Co., Ltd. 1.06 g
Inorganic particle dispersion: containing 30% by mass of silicon oxide, methyl ethyl ketone-dispersed silica sol (manufactured by Nissan Chemical Co., Ltd., trade name IPA-ST-ZL), average primary particle size of silicon oxide particles = 100 nm
14.28g
Methyl ethyl ketone 0.52g
The above additives were sequentially mixed and stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1.0 μm to prepare a stress relaxation layer coating solution 4.

(Preparation of coating solution 5 for stress relaxation layer)
UV curable resin: Beamset 575CB, urethane acrylate resin, 5.02 g made by Arakawa Chemical Industries, Ltd.
Photoinitiator: Irgacure 184, Ciba Japan 0.25g
Inorganic particle dispersion: containing 30% by mass of silicon oxide, methyl ethyl ketone-dispersed silica sol (manufactured by Nissan Chemical Co., Ltd., trade name MEK-ST), average primary particle diameter of silicon oxide particles = 10 nm
30.45g
Methyl ethyl ketone 0.52g
The above additives were sequentially mixed and stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1.0 μm to prepare a stress relaxation layer coating solution 5.

  Table 1 shows details and characteristic values of each stress relaxation layer coating solution prepared as described above.

  In addition, each characteristic value described in Table 1 was obtained by measurement according to the following method.

[Measurement of surface hardness of surface layer and stress relaxation layer]
The surface hardness when the surface layer or the stress relaxation layer was formed using the surface layer coating solution or each stress relaxation layer coating solution was measured according to the following method.

(Measurement of surface hardness of surface layer)
Using a coating solution for each surface layer on a resin base material, coating with a wire bar under the condition that the dry film thickness is 1.0 μm, drying at 90 ° C. for 30 seconds, and curing reaction at 120 ° C. for 30 minutes. It was.

  Next, the surface hardness of the formed surface layer was measured by nanoindentation. The hardness (H) was measured by attaching a Triscope from Hystron to a Nanoscope III from Digital Instruments. For the measurement, a triangular pyramid type diamond indenter called a Belkovic indenter (tip ridge angle 142.3 °) was used as an indenter. A triangular pyramid-shaped diamond indenter was applied to the sample surface at a right angle, a load was gradually applied, and the load was gradually returned to 0 after reaching the maximum load. A value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion was calculated as nanoindentation hardness (H). The maximum load condition at this time was 100 μN.

(Measurement of surface hardness of stress relaxation layer)
On the resin substrate, using each stress relaxation layer coating solution, with a wire bar under the condition that the dry film thickness is 10.0 μm, after drying at 90 ° C., using an ultraviolet lamp, The stress relaxation layer was formed by curing with an illuminance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² . Next, measurement by nanoindentation was performed in the same manner as the surface height measurement of the upper layer.

(Measurement of inorganic particle filling rate)
In each stress relaxation layer coating solution, the ratio of the inorganic particles to the solid content (components other than the solvent) (solid content ratio, particle filling rate) was measured. In addition, since active energy ray hardening resin shrinks simultaneously with hardening by reaction by irradiation of active energy ray, it calculated | required with the filling rate measuring method (volume analysis method) shown below.

<Filling rate measurement method (volume analysis method)>
The filling rate of the inorganic particles in the stress relaxation layer after drying was measured by the following method. After applying each coating solution on the resin base material by wet coating method to form a stress relaxation layer, the stress relaxation layer is peeled off from the resin base material to measure the total volume, and then the resin component is dissolved. The volume of the inorganic particles was measured, and the filling rate (volume%) of the inorganic particles was determined from the measured values.

<< Production of laminate with functional layer >>
[Resin substrate]
As the resin substrate, a polyethylene terephthalate film (Teijin-DuPont film, hereinafter abbreviated as PET) having a thickness of 100 μm was used.

[Preparation of Sample 1]
Sample 1 which is a laminate with a functional layer was produced according to the following method.

  On the above resin substrate, using the surface layer coating solution 3, coating with a wire bar under the condition that the dry film thickness is 1.0 μm, drying at 90 ° C. for 30 seconds, and curing reaction at 120 ° C. for 30 minutes. Then, a surface layer was formed, and Sample 1 was produced.

[Preparation of Sample 2]
On the resin base material, using the stress relaxation layer coating solution 2, coating with a wire bar under the condition that the dry film thickness is 4.0 μm, drying at 90 ° C., and then using an ultraviolet lamp to irradiate the irradiated part Was cured with an illuminance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² to form a first layer of a stress relaxation layer. Next, using the stress relaxation layer coating solution 5, on the condition that the dry film thickness is 4.0 μm, coating with a wire bar and drying at 90 ° C., using an ultraviolet lamp, The second layer of the stress relaxation layer was formed by curing with an illuminance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² . Next, using the stress relaxation layer coating solution 3 thereon, coating with a wire bar under the condition that the dry film thickness is 4.0 μm, drying at 90 ° C., and using an ultraviolet lamp, The irradiance was 100 mW / cm ² , the irradiation amount was 80 mJ / cm ² , and the third layer of the stress relaxation layer was formed to obtain a stress relaxation layer composed of three layers.

  Next, using the surface layer coating solution 4, the coating, drying, and curing reactions were performed in the same manner as Sample 1 to prepare Sample 2.

[Preparation of Samples 3-6, 8, 10]
In the preparation of Sample 2, the stress relaxation layer was formed in the same manner except that the number of layers to be laminated, each dry film thickness (μm), and the type of surface coating liquid were changed to the conditions described in Table 2. 3-6, 8, and 10 were produced.

[Preparation of Samples 7 and 9]
In the preparation of Samples 6 and 8 described above, each coating solution for the stress relaxation layer was applied simultaneously on the resin substrate using a slide hopper type coating apparatus capable of simultaneous application, and the state was maintained for 10 seconds. After drying at 90 ° C., Samples 7 and 9 were prepared in the same manner except that an ultraviolet lamp was used and the irradiation part was cured with an illuminance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² .

[Preparation of Sample 11]
Sample 11 was prepared in the same manner as in preparation of Sample 2 except that the formation of the stress relaxation layer was changed to the following method.

(Formation of stress relaxation layer)
On the resin base material, using a stress relaxation layer coating solution 5, coated with a wire bar under the condition that the dry film thickness is 4.0 μm, dried at 90 ° C., and then irradiated with an ultraviolet lamp. Was cured with an irradiance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² to form the first layer (B layer unit) of the stress relaxation layer. Next, using the stress relaxation layer coating liquid 3 thereon, coating with a wire bar under the condition that the dry film thickness is 2.0 μm, drying at 90 ° C., and then using an ultraviolet lamp, The second layer (A layer unit) of the stress relaxation layer was formed by curing with an illuminance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² . Next, using the stress relaxation layer coating solution 5, the coating was applied with a wire bar under the condition that the dry film thickness was 2.0 μm, and dried at 90 ° C. Then, using an ultraviolet lamp, The third layer (B layer unit) of the stress relaxation layer was formed by curing with an illuminance of 100 mW / cm ² and an irradiation amount of 80 mJ / cm ² . Next, using the stress relaxation layer coating solution 3 thereon, coating with a wire bar under the condition that the dry film thickness is 4.0 μm, drying at 90 ° C., and using an ultraviolet lamp, Curing with an illuminance of 100 mW / cm ² and an irradiation dose of 80 mJ / cm ² to form a fourth layer (A layer unit) of the stress relaxation layer, and producing a stress relaxation layer in which the A layer and the B layer are alternately laminated did.

  Next, using the surface layer coating solution 4, coating, drying, and curing reactions were performed in the same manner as in Sample 1 to prepare Sample 11.

[Preparation of Samples 12-15, 17, 19]
In the preparation of Sample 11, the stress relaxation layer was formed in the same manner except that the number of layers to be laminated, each dry film thickness (μm), and the type of surface layer coating solution were changed to the conditions described in Table 3. Samples 12 to 15, 17, and 19 were prepared.

[Production of Samples 16 and 18]
In the preparation of the samples 14 and 17, the coating liquids of the first to fourth layers of the stress relaxation layer were simultaneously applied on the resin substrate using a slide hopper type coating apparatus capable of simultaneous application. The sample was maintained for 10 seconds, dried at 90 ° C., and then cured using an ultraviolet lamp, the irradiation portion was illuminated with an illuminance of 100 mW / cm ² and an irradiation dose of 80 mJ / cm ^2. 16 and 18 were produced.

<< Evaluation of laminate with functional layer >>
The following evaluation was performed about the produced laminated body with a functional layer (samples 1-19).

(Evaluation of adhesion)
Each of the prepared laminates with functional layers was evaluated for adhesion by a cross-cut test based on JIS K 5400.

  On the surface on which each layer of each layer with functional layers was formed, 11 cuts of 90 ° with respect to the surface were made with a single-edged razor blade in vertical and horizontal directions at 1 mm intervals to create 100 1 mm square grids. . Paste commercially available cellophane tape on this grid, peel one end vertically by hand, measure the ratio of the peeled area to the tape area pasted from the score line, and according to the following evaluation criteria Adhesion was evaluated. Moreover, about the sample which raise | generated peeling, confirmation of the peeled layer was also performed simultaneously.

<Evaluation rank>
5: No peeling was observed 4: The area of the peeled layer was 1% or more and less than 5% 3: The area of the peeled layer was 5% or more and less than 10% 2: of the peeled layer The area was 10% or more and less than 20% 1: The area of the peeled layer was 20% or more <Peeling position>
a: Peeling occurred between the resin base material and the upper layer b: Peeling occurred between the middle layers of the stress relaxation layer c: Peeling occurred between the outermost surface layer and the surface layer of the stress relaxation layer −: Peeling Neither occurred (evaluation of scratch resistance)
Using the steel wool (Bonster # 0000, 2 cm × 2 cm) with a friction tester HEIDON-14DR, the load (9.8 N, 2 cm × 2 cm) was applied to the surface of each of the prepared laminates with functional layers (surface layer forming surface side). After carrying out the rubbing treatment 20 times under the condition of 15 mm / min, the rubbing range was observed with a loupe, and the scratch resistance was evaluated according to the following criteria.

A: No generation of scratches is observed. O: Generation of scratches is 1 or more and 5 or less. Δ: Generation of scratches is 6 or more and 15 or less. X: Generation of scratches is 16 or more. It is 25 or less. XX: Generation of scratches is 26 or more. Table 4 shows the results obtained as described above.

  As is clear from the results shown in Table 4, it can be seen that the laminate with a functional layer having a layer structure defined in the present invention is superior in adhesion and scratch resistance to the comparative example.

Example 2
<Production of molded body>
(Preparation of lens mold molded body L)
As shown in FIG. 4 a), samples 1 to 19 (stacked body 1 with a surface layer in FIG. 4), which are the above-mentioned stacked layers with a functional layer, are fixed with a clamp 201 with the surface layer facing up. To do. Next, as shown in FIG. 4 b), using the heaters 203 arranged above and below the surface layered laminate 1, the surfaced layered body 1 is drawn down (“sag of the surface layered layered body due to its own weight during heating”). )). Next, as shown in FIG. 4 c), the laminate with surface layer 1 and the lens mold 202 are brought into contact with each other from below the laminate with surface layer 1. Next, as shown in FIG. 4 d), the lower layer of the lens mold 202 is depressurized in the X direction so that the laminate with surface layer 1 and the lens mold 202 are adhered to each other. Next, as shown in e) of FIG. 4, the laminated body 1 with the surface layer is cooled and solidified, the lens mold 202 is released, the clamp 201 is removed, and the molding is performed as shown in f) of FIG. Unnecessary extra portions were trimmed to obtain lens-shaped molded bodies L1 (lens-type laminate with surface layer 1) having a surface layer on the convex surface side.

  Next, as shown in FIG. 5, after the lens mold molded body L <b> 1 prepared above is placed in the first injection mold 10, the second injection mold 9 is overlaid, and polycarbonate is injected into the cavity from the injection port 11. Each lens mold molding provided with a functional laminate on the convex side of the surface of the polycarbonate resin 12 as shown in FIG. 5 by injecting the resin 12 at a resin temperature of 300 ° C., a mold temperature of 90 ° C., and an injection pressure of 10 MPa. Body L was obtained.

<< Evaluation of each molded body L >>
(Evaluation of scratch resistance)
Using the steel wool (Bonster # 0000, 2 cm × 2 cm) with a friction tester HEIDON-14DR, the load (9.8 N, 2 cm × 2 cm) was applied to the surface of each of the prepared laminates with functional layers (surface layer forming surface side). After scratching 20 times under the condition of 15 mm / min, the scratch range was observed with a loupe, and scratch resistance evaluation 1 was performed according to the following criteria.

A: No generation of scratches is observed. O: Generation of scratches is 1 or more and 5 or less. Δ: Generation of scratches is 6 or more and 15 or less. X: Generation of scratches is 16 or more. It is 25 or less. XX: The number of scratches is 26 or more (Evaluation of substrate followability)
The state of the surface layer of the obtained molded body L was observed with a magnifying glass and visually, and the substrate followability was evaluated according to the following criteria.

◎: Good mold reproduction, no cracks or wrinkles observed ○: Mold reproduction is good, but very weak cracks or wrinkles are observed △: Either crack or wrinkle Failure occurrence is recognized. X: Failure occurrence of both cracks and wrinkles is recognized. Table 5 shows the results obtained as described above.

  As is clear from the results shown in Table 5, the laminate sample with a functional layer for molding obtained in the configuration defined in the present invention is superior in the scratch resistance and the substrate followability to the comparative sample. I understand that.

DESCRIPTION OF SYMBOLS 1 Laminated body with a functional layer 2 Resin base material 3, 3-1, 3-2, 3A-1, 3A-2, 3B-1, 3B-2, 3-i, 3-ro, 3A-i, 3A -B, 3B-I, 3B-B Stress relaxation layer 4 Surface layer 5 Release layer 9 Second injection mold 10 First injection mold 11 Injection port 12 Polycarbonate resin 201 Clamp 202 Lens mold 203 Heater B Resin base L1 Lens mold molding body

Claims (9)

In a laminate with a functional layer in which a stress relaxation layer and a surface layer are laminated in this order on at least one surface of a resin substrate, the surface layer is composed of at least a silazane and an organic polymer, and the stress relaxation layer in contact with the surface layer A layered product with a functional layer, wherein the hardness H by nanoindentation of the layer is equal to or lower than the hardness H by nanoindentation of the surface layer. The stress relaxation layer is composed of two or more layers having different hardness H, and the hardness H decreases from the stress relaxation layer in contact with the surface layer toward the stress relaxation layer in contact with the resin substrate. A laminate with a functional layer described in 1. 2. The functional layer according to claim 1, wherein the stress relaxation layer has a configuration in which the hardness H continuously decreases in a film thickness direction from a region in contact with the surface layer to a region in contact with the resin base material. Laminated body. 2. The stress relaxation layer is composed of two or more layers having different particle concentrations, and the particle concentration decreases from the stress relaxation layer in contact with the surface layer toward the stress relaxation layer in contact with the resin substrate. Laminated body with functional layer. The layered product with a functional layer according to claim 1, wherein the stress relaxation layer has a particle concentration that continuously decreases in a film thickness direction from a region in contact with the surface layer to a region in contact with the resin base material. The stress relaxation layer has a structure in which two layers having different hardness H are alternately laminated. When the layer group having a high hardness H is an A layer unit and the layer group having a low hardness H is a B layer unit, the A layer At least one layer unit of the unit and the B layer unit is constituted by at least two layers having different dry film thicknesses, and when the A layer unit is constituted by layers having different dry film thicknesses, the A layer unit is constituted. When the dry film thickness of each layer increases toward the surface layer and the B layer unit is composed of layers having different dry film thicknesses, the dry film thickness of each layer constituting the B layer unit is 2. The laminated layer with a functional layer according to claim 1, wherein the total thickness ΣAh of the dry layer thickness of the A layer unit is equal to the total sum of the dry thickness ΣBh of the B layer unit. body. The stress relaxation layer has a structure in which two layers having different particle concentrations are alternately laminated. When the layer group having a high particle concentration is an A layer unit and the layer group having a low particle concentration is a B layer unit, the A At least one layer unit of the layer unit and the B layer unit is composed of at least two layers having different dry film thicknesses, and when the A layer unit is composed of layers having different dry film thicknesses, When the dry film thickness of each layer constituting increases toward the surface layer and the B layer unit is composed of layers having different dry film thicknesses, the dry film thickness of each layer constituting the B layer unit is The functional layer according to claim 1, wherein the total thickness ΣAh of the dry layer thickness of the A layer unit is equal to the total thickness ΣBh of the dry layer thickness of the B layer unit. Laminated body. The layered product with a functional layer according to claim 1, wherein the silazane concentration in the surface layer is 50% by mass or more and 95% by mass or less. The resin base material is a resin film, and the laminate with a functional layer according to any one of claims 1 to 8 is loaded on one or both surfaces of the mold so that the surface layer is on the mold side. After that, a molding material made of synthetic resin is injected and injected onto the laminate with a functional layer in a mold, and the laminate with a functional layer and the molding material are laminated and integrated. Molded body.

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