JP2010253767A - Hard coat molded article and method of manufacturing the same, and active energy ray curable coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone based hard coat molded article excellent in abrasion resistance and crack resistance which can be formed in a short time. <P>SOLUTION: The molded article has a silicone-based hard coat layer cured by an active energy ray on the surface of a base material. In the hard coat molded article, an area ratio A1/A2 of a peak area A1 of an infrared absorption spectrum resulting from a cyclic siloxane bond of the hard coat layer to a peak area A2 of the infrared absorption spectrum resulting from a straight-chain siloxane bond is 0.83 or larger and 0.97 or smaller, and an ratio A3/(A1+A2) of a peak area A3 of the infrared absorption spectrum resulting from a silanol group to the sum (A1+A2) of A1 and A2 is 0.020 or larger and 0.028 or smaller. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a silicon-based hard coat molded article excellent in scratch resistance and crack resistance, a method for producing the same, and an active energy ray-curable coating composition for forming a hard coat.

  In recent years, transparent plastic materials such as acrylic resin and polycarbonate resin, which are excellent in crush resistance and light weight, have been widely used as an alternative to transparent glass. However, since the transparent plastic material has a lower surface hardness than glass, it has a problem that the surface is easily damaged.

  Thus, many attempts have been made to improve the scratch resistance of plastic materials. As one of the most common methods, a method of forming a hard coat layer made of an inorganic polymer having a siloxane bond on the surface of a substrate by utilizing hydrolysis of an alkoxysilane compound and subsequent condensation reaction is widely known. (See Patent Documents 1 and 2). However, these methods have a problem in productivity because a heating time of several tens of minutes to several hours is required to form a hard coat layer.

  In order to solve these problems, for example, a siloxane oligomer having a siloxane skeleton in the molecule and having a reactive silanol group, alkoxysilane group, etc. and an active energy ray-sensitive cationic polymerization initiator are contained as essential components. And the composition which hardens | cures by active energy ray irradiation and forms a hard-coat layer in a short time is proposed (for example, refer patent document 3, 4). Specifically, a siloxane bond is formed between a silanol group and an alkoxysilane group using an acid generated from a cationic polymerization initiator as a catalyst by applying such a composition to a substrate and irradiating active energy rays such as ultraviolet rays. Is formed to form a cured film. According to this method, a film can be formed in a short time. However, depending on the structure of the siloxane oligomer used and the irradiation method of the active energy ray, the physical properties of the obtained cured film are greatly changed, and physical properties such as scratch resistance are obtained. There was a problem that was not expressed.

  On the other hand, Patent Document 5 proposes a method for evaluating the scratch resistance from the infrared absorption spectrum of a cured coating. According to this method, a cured film having practical scratch resistance can be obtained by setting the infrared absorption spectrum of the cured film within a specific range. As a result of investigations by the present inventors, this method was effective for a cured film formed by advancing the curing reaction by heating or the like as in Patent Documents 1 and 2. However, in a cured film formed in a short time by irradiation with active energy rays, the shrinkage stress increases due to a rapid polycondensation reaction, so that the scratch resistance is good, but cracks tend to occur, and it is practical. It was difficult to form a film. That is, normally, a hard coat layer obtained by irradiating active energy rays with a siloxane oligomer and an active energy ray-sensitive cationic polymerization initiator as the main components increases the crosslink density by sufficiently proceeding with the condensation reaction, and is excellent. Although the scratch resistance is exhibited, the amount of condensation stress is increased at the same time and the crack resistance is lowered, and the scratch resistance and the crack resistance are in a trade-off relationship.

JP 48-26822 A JP 55-94971 A JP-A-53-97098 JP 56-106958 A JP 2003-41033 A

  The present invention has been made to solve the above-described problems in the prior art. That is, an object of the present invention is to provide a silicon-based hard coat molded article that can be formed in a short time and has excellent scratch resistance and crack resistance.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have resulted from the peak area A1 of the infrared absorption spectrum due to the cyclic siloxane bond and the linear siloxane bond in the infrared absorption spectrum of the hard cord molded product. Area ratio A1 / A2 with respect to A2 of the infrared absorption spectrum (hereinafter referred to as area ratio A1 / A2), and the sum of absorption due to the siloxane bond (A1 + A2) and the infrared absorption spectrum due to the silanol group By making the ratio A3 / (A1 + A2) to the peak area A3 of (A1 / A2) (hereinafter, referred to as the area ratio A3 / (A1 + A2)) a specific value, both scratch resistance and crack resistance can be achieved. The headline, the present invention has been reached.

That is, the present invention
A molded product having a silicon-based hard coat layer cured by active energy rays on the surface of the substrate,
The area ratio A1 / A2 between the peak area A1 of the infrared absorption spectrum caused by the cyclic siloxane bond of the silicon-based hard coat layer and the peak area A2 of the infrared absorption spectrum caused by the linear siloxane bond is 0.83 or more, 0 The ratio A3 / (A1 + A2) between the sum of A1 and A2 (A1 + A2) and the peak area A3 of the infrared absorption spectrum caused by the silanol group is 0.020 or more and 0.028 or less. Code molded product.

  The inventors have also found that a hard cord molded product satisfying the above conditions can be produced by using a siloxane oligomer having a specific structure, and the present invention has been achieved.

That is, the present invention
(A) The area ratio A4 / A5 between the peak area A4 of the infrared absorption spectrum caused by the cyclic siloxane bond and the peak area A5 of the infrared absorption spectrum caused by the linear siloxane bond is 1.83 or more and 2.03 or less. A siloxane oligomer having an area ratio A6 / (A4 + A5) of 0.300 or more and 0.360 or less between the sum of A4 and A5 (A4 + A5) and the peak area A6 of the infrared absorption spectrum caused by the silanol group;
(B) An active energy ray-sensitive cationic polymerization initiator and an active energy ray-curable coating composition that is applied to the surface of the base material and irradiated with active energy rays to be crosslinked and cured. It is a manufacturing method.

The present invention also provides:
The (A) siloxane oligomer is
(C) a siloxane oligomer in which the area ratio A4 / A5 is 1.83 or more and 2.50 or less, and the area ratio A6 / (A4 + A5) is 0.200 or more and 0.300 or less;
(D) a mixture of the area ratio A4 / A5 is 1.50 or more and less than 1.83, and the area ratio A6 / (A4 + A5) is 0.250 or more and 0.380 or less. It is a manufacturing method of a certain hard coat molded article.

Furthermore, the present invention provides
(A) The area ratio A4 / A5 between the peak area A4 of the infrared absorption spectrum caused by the cyclic siloxane bond and the peak area A5 of the infrared absorption spectrum caused by the linear siloxane bond is 1.83 or more and 2.03 or less. A siloxane oligomer having an area ratio A6 / (A4 + A5) of 0.300 or more and 0.360 or less between the sum of A4 and A5 (A4 + A5) and the peak area A6 of the infrared absorption spectrum caused by the silanol group;
(B) An active energy ray-curable coating composition containing an active energy ray-sensitive cationic polymerization initiator.

Furthermore, the present invention provides
The (A) siloxane oligomer is
(C) a siloxane oligomer in which the area ratio A4 / A5 is 1.83 or more and 2.50 or less, and the area ratio A6 / (A4 + A5) is 0.200 or more and 0.300 or less;
(D) a mixture of the area ratio A4 / A5 is 1.50 or more and less than 1.83, and the area ratio A6 / (A4 + A5) is 0.250 or more and 0.380 or less. A curable coating composition.

  According to the present invention, by setting the ratio of the cyclic siloxane bond to the linear siloxane bond within a specific range, the cyclic siloxane bond contained in the composition can provide appropriate flexibility and improve crack resistance. Furthermore, by setting the ratio of siloxane bonds and silanol groups, which are indicators of the reaction rate, to a specific range and curing to a crosslinking density sufficient to develop scratch resistance, both crack resistance and scratch resistance are achieved. A silicon-based hard coat molded product can be obtained.

It is a graph which shows an example of the infrared absorption spectrum of a silicon-type hard-coat layer. It is a graph which shows an example of the infrared absorption spectrum of a siloxane oligomer. 2 is a graph showing an infrared absorption spectrum of the silicon-based hard coat layer obtained in Example 1. FIG. 5 is a graph showing an infrared absorption spectrum of a silicon-based hard coat layer obtained in Comparative Example 1. 6 is a graph showing an infrared absorption spectrum of a silicon-based hard coat layer obtained in Comparative Example 2.

(Hard code molded product)
The hard coat molded article of the present invention has a silicon-based hard coat layer cured with active energy rays on the surface or front and back surfaces of a substrate.

  Here, various materials such as plastic, metal, can, paper, wood material, inorganic material, electrodeposition coating plate, and laminate plate are used as the base material. In particular, plastic base materials such as polymethyl methacrylate, polycarbonate, polystyrene, and polymethacryl styrene have a low surface hardness and are easily scratched. Therefore, it is necessary to provide a hard coat layer on the surface.

  It is preferable to form a primer layer between the base material and the silicon hard coat layer on the base material to which the silicon hard coat layer is difficult to adhere. Although it does not specifically limit as a primer layer, The layer obtained by photocuring the composition containing an active energy ray radically polymerizable vinyl compound and an active energy ray sensitive radical polymerization initiator is preferable. More specifically, examples of the base material such as polycarbonate may include a base material in which a primer layer is formed with a composition containing a polyfunctional (meth) acrylate and an active energy ray-sensitive radical polymerization initiator. The present invention is not limited to these. The polyfunctional (meth) acrylate here is a compound having two or more (meth) acryloyloxy groups in the molecule. Moreover, (meth) acrylate shows an acrylate and a methacrylate.

(Structure of silicon hard coat layer)
Next, the silicon hard coat layer will be described. In the silicon-based hard coat layer of the present invention, the area ratio A1 / A2 between the peak area A1 of the infrared absorption spectrum due to the cyclic siloxane bond and the peak area A2 of the infrared absorption spectrum due to the linear siloxane bond is 0.83. The ratio A3 / (A1 + A2) between the sum of A1 and A2 (A1 + A2) and the peak area A3 of the infrared absorption spectrum caused by the silanol group is 0.020 or more and 0.028 or less. It is.

  By setting the area ratio A1 / A2 between the cyclic siloxane bond and the linear siloxane bond to 0.83 or more, sufficient cyclic flexibility is generated by the contained cyclic siloxane bond, and crack resistance can be improved. Moreover, by setting it as 0.97 or less, the influence of the abrasion-resistant fall by inclusion of a cyclic siloxane bond can be made small, and sufficient abrasion resistance can be obtained.

  Further, by setting the area ratio A3 / (A1 + A2) to 0.020 or more, the amount of curing shrinkage caused by the progress of the polycondensation reaction is small, and the hard coat layer is less likely to be cracked. By making it below, the polycondensation reaction proceeds sufficiently and sufficient scratch resistance is obtained.

(How to determine the peak area of the infrared absorption spectrum of a silicon hard coat layer)
Here, how to determine the peak areas A1, A2, and A3 of the infrared absorption spectrum caused by the cyclic siloxane bond, the linear siloxane bond, and the silanol group of the silicon hard coat layer will be described.

  The infrared absorption spectrum of the silicon-based hard coat layer is measured by an FT-IR total reflection method (ATR: Attenuated Total Reflectance). FIG. 1 is an example of an infrared absorption spectrum of a silicon-based hard coat layer measured by this method.

Siloxane bond has a absorption in 960～1240Cm ^-1, of which a high wave number side than 1050 cm ^-1 in the cyclic siloxane bond, lower wavenumber side is attributed to a linear siloxane bonds. The cyclic siloxane bond is a siloxane bond that forms a cyclic structure, and the linear siloxane bond is a ring that does not form a cyclic structure.

In Figure 1, a line segment connecting the point B indicates the absorbance at A and 960 cm ^-1 that indicates the absorbance at 1240 cm ^-1 and a line segment AB, and the point C to a point at 1050 cm ^-1 on the line segment AB To do. The peak area A1 resulting from the cyclic siloxane bond is an area surrounded by the line segment AC and the spectrum curve therebetween. Moreover, the peak area A2 resulting from the linear siloxane bond is an area surrounded by the line segment CB and the spectrum curve therebetween.

Moreover, the silanol group has a absorption in 860～960Cm ^-1, when a line segment connecting the point D shows the absorbance at point B and 860 cm ^-1 and a line segment BD, peak area attributed to silanol groups A3 Is the area surrounded by the line segment BD and the spectral curve between them.

As the measurement conditions, a Ge crystal may be used with an incident angle of 45 ° and a single reflection measurement. For example, an FT-IR (trade name: “NEXUS470”, manufactured by Thermo Nicolet Co., Ltd.) and an ATR measurement accessory (product) A name “FOUNDATION ThunderDome” (Spectratech Co., Ltd.) is attached, and measurement is performed with a resolution of 4 cm ⁻¹ and 32 integrations. The peak area can be obtained by an arbitrary method, for example, using an integration tool of FT-IR analysis software (trade name “OMNIC”, manufactured by Thermo Nicolay Co., Ltd.).

(Structure of siloxane oligomer (A))
The silicon-based hard coat layer has an active energy ray-curable coating composition containing a siloxane oligomer (A) having a specific structure and an active energy ray-sensitive cationic polymerization initiator (B) on the substrate surface. It can be formed by coating, irradiating with active energy rays and curing by crosslinking.

  In the siloxane oligomer (A) used in the present invention, the area ratio A4 / A5 between the peak area A4 of the infrared absorption spectrum caused by the cyclic siloxane bond and the peak area A5 of the infrared absorption spectrum caused by the linear siloxane bond is 1. The area ratio A6 / (A4 + A5) between the sum of A4 and A5 (A4 + A5) and the peak area A6 of the infrared absorption spectrum caused by the silanol group is from 0.300 to 0.360. The following is preferable.

  The value of the area ratio A1 / A2 in the silicon-based hard coat layer has a correlation with the value of the area ratio A4 / A5 in the siloxane oligomer (A) to be used. By using the siloxane oligomer (A) having an area ratio A4 / A5 of 1.83 or more and 2.03 or less, the area ratio A1 / A2 of the hard coat layer after curing is made 0.83 or more and 0.97 or less. It is possible to improve crack resistance and scratch resistance. Further, by using the siloxane oligomer (A) having an area ratio A6 / (A4 + A5) of 0.300 or more and 0.360 or less, the area ratio A3 / (A1 + A2) of the hard coat layer is 0.020 or more and 0.028. The increase in shrinkage stress can be further suppressed, and cracks can be made difficult to occur in the hard coat layer.

(How to find the peak area of infrared absorption spectrum of siloxane oligomer)
Here, how to obtain the peak areas A4, A5, and A6 of the infrared absorption spectrum caused by the cyclic siloxane bond, the linear siloxane bond, and the silanol group of the siloxane oligomer will be described.

  The infrared absorption spectrum of the siloxane oligomer is measured by applying a siloxane oligomer solution on a substrate, sufficiently drying the solvent at room temperature, and then measuring the total reflection method (ATR; Attenuated Total Reflectance) using FT-IR. FIG. 2 is an example of an infrared absorption spectrum of a siloxane oligomer measured by this method.

As described above, the siloxane bond has absorption at 960 to 1240 cm ⁻¹ , of which the higher wave number than 1050 cm ⁻¹ is attributed to the cyclic siloxane bond, and the lower wave number is attributed to the linear siloxane bond.

2, a line segment connecting the point F indicates the absorbance at E and 960 cm ^-1 that indicates the absorbance at 1240 cm ^-1 and the line segment EF, and the point a point in 1050 cm ^-1 on the line EF G To do. The peak area A4 resulting from the cyclic siloxane bond is an area surrounded by the line segment EG and the spectrum curve therebetween. Moreover, the peak area A5 resulting from the linear siloxane bond is an area surrounded by the line segment GF and the spectrum curve therebetween.

Moreover, the silanol group has a absorption in 860～960Cm ^-1, when a line segment connecting the point H which shows the absorbance at point F and 860 cm ^-1 line segment FH, peak area attributed to silanol groups A6 Is the area surrounded by the line segment FH and the spectral curve between them.

  The measurement conditions are the same as those for the silicon hard coat layer.

(Synthesis method of siloxane oligomer (A))
The siloxane oligomer (A) can be obtained by hydrolyzing and condensing organosiloxanes and alkyl silicates.

  By using the siloxane oligomer (A), which is obtained by hydrolyzing and condensing organosilanes and alkyl silicates in advance and forming a crosslinked structure between molecules to increase the molecular weight, the curability and physical properties of the obtained hard coat layer can be improved. Can be improved. Moreover, by using the high molecular weight siloxane oligomer (A), shrinkage due to polycondensation during curing and the stress generated therewith can be reduced, and as a result, crack reduction and substrate adhesion can be improved.

The siloxane oligomer (A) is represented by, for example, 85 to 95 mol% of an organosilane represented by the following formula (1), 5 to 15 mol% of an organosilane represented by the following formula (2), and the following formula (3). It is obtained by hydrolyzing and condensing an organosilane or an alkyl silicate represented by the following formula (4) 0 to 10 mol%.
CH ₃ Si (OR ¹ ) ₃ (1)
C ₆ H ₅ Si (OR ² ) ₃ (2)
(In formulas (1) and (2), R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms.)
R ³ _a Si (OR ⁴ ) _4-a (3)
(In the formula (3), R ³ is an organic group having 1 to 10 carbon atoms, R ⁴ is of .a 1-3 showing the acyl group of 1 to 4 alkyl groups or C1-5 atoms Represents an integer, provided that when a is 1, R ³ represents an organic group other than a methyl group or a phenyl group.)

(In the formula (4), R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. Represents an integer of ~ 20).

  The organosilane represented by the formula (1) is a trifunctional organosilane in which one methyl group is bonded to a silicon atom, and is a main component in the siloxane oligomer (A). By containing this in an amount of 85 to 95 mol%, the flexibility of the hard coat layer can be improved and the occurrence of cracks can be reduced as compared with the case where a tetrafunctional alkyl silicate is used as a main component. Furthermore, since the methyl group has less steric hindrance, a denser siloxane network is formed, and a hard coat layer with good scratch resistance can be obtained.

In the formula (1), the alkyl group of 1 to 5 carbon atoms for R ^1, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, n- pentyl group. Examples of the acyl group having 1 to 4 carbon atoms include formyl group, acetyl group, propionyl group, and butyryl group. R ¹ is preferably a methyl group or an ethyl group from the viewpoint of easy production and a high hydrolysis rate.

  Specific examples of the organosilanes represented by the formula (1) include, but are not limited to, methyltrimethoxysilane and methyltriethoxysilane.

  The organosilane represented by the formula (2) is a trifunctional organosilane in which one phenyl group is bonded to a silicon atom. By blending this with 5 mol% or more in the siloxane oligomer (A), the flexibility of the hard coat layer can be improved, the occurrence of cracks can be reduced, and the adhesion to the substrate can be improved. Moreover, by making a compounding quantity 15 mol% or less, excessive softening can be suppressed and a hard-coat layer with favorable abrasion resistance can be obtained.

In the formula (2), R ² can be the same as R ¹ , and a methyl group or an ethyl group is preferable from the viewpoint of easy production and a high hydrolysis rate.

  Specific examples of the organosilanes represented by the formula (2) include phenyltrimethoxysilane and phenyltriethoxysilane, but are not limited thereto.

In the formula (3), as the organic group having 1 to 10 carbon atoms of R ³ , a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, Cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, formyl group, acetyl group, propionyl group, butyryl group, vinyl group, glycidyl group, acryloyl group, methacryloyl group, styryl group, A phenyl group etc. are mentioned. However, when a is 1, R ³ represents an organic group other than a methyl group or a phenyl group. Among these, as R ³ , a methyl group, an ethyl group, and the like are preferable from the viewpoint of less steric hindrance. R ⁴ can be the same as R ¹ and is preferably a methyl group or an ethyl group from the viewpoint of easy production and a high hydrolysis rate.

  Specific examples of the organosilanes represented by the formula (3) include vinyltriethoxysilane, vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 2- (3,4-epoxy. (Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyl Triethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane Triethyl silane, trimethyl silane, but triethyl silane and the like, but is not limited thereto. Of these, dimethyldimethoxysilane, dimethyldiethoxysilane, and the like are preferable from the viewpoint of less steric hindrance. In the present invention, these can be used as one kind or a mixture of two or more kinds.

In the formula (4), R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. These groups may be the same or different. n represents the number of repeating units of the alkyl silicate, and is an integer of 1-20. When n is larger than 20, gelation tends to occur during hydrolysis and condensation. It is preferable that n is an integer of 1 to 10 from the viewpoint of obtaining good curability and physical properties of the film and being difficult to gel. R ⁵ , R ⁶ , R ⁷ and R ⁸ can be the same as R ¹ , but a methyl group and an ethyl group are preferred.

Specific examples of the alkyl silicates represented by the formula (4) include methyl silicates in which R ^{5 to} R ⁸ are methyl groups, ethyl silicates in which R ^{5 to} R ⁸ are ethyl groups, and R ^{5 to} R ⁸ are isopropyl. isopropyl silicate is a group, R ⁵ to R ⁸ is a n- propyl group n- propyl silicate, R ⁵ to R ⁸ is a n- butyl group n- butyl silicate, R ⁵ to R ⁸ is n- pentyl group N-pentyl silicate, R ^{5 to} R ⁸ are acetyl silicates, and the like, but are not limited thereto. Among these, methyl silicate and ethyl silicate are preferable because they are easily available and have a high hydrolysis rate.

  Hydrolysis can be performed using known methods. For example, the organosilane is mixed with an alcohol, and water (for example, 1 to 1000 mol of water with respect to 1 mol of the organosilane) and an acid such as hydrochloric acid or acetic acid are added to make the solution acidic (for example, pH 2 to 4). ) And stirring.

  In addition, there is a method in which the organosilane is mixed with an alcohol, and water (for example, 1 to 1000 mol per 1 mol of the organosilane) is added and heated (for example, 30 to 100 ° C.). The alcohol generated during the hydrolysis may be distilled out of the system. Condensation following hydrolysis can be allowed to proceed by leaving the organosilanes in the hydrolyzed state. At that time, the progress of the condensation can be accelerated by heating (for example, 30 to 100 ° C.) or controlling the pH to be near neutral (for example, pH 6 to 7). The water generated during the condensation may be distilled out of the system.

  The ratio of the organosilane to the alkyl silicate is not particularly limited as long as the crack resistance of the hard coat layer is good, but the alkyl silicate is preferably 0 mol to 1 mol with respect to 1 mol of the organosilane. More preferred is 1 mole.

(Blend of siloxane oligomer)
The siloxane oligomer (A) may be used alone as long as the area ratio A4 / A5 and the area ratio A6 / (A4 + A5) are within the above ranges. However, if the area ratio A4 / A5 is in the range of 1.83 or more and 2.03 or less, the area ratio A6 / (A4 + A5) tends to be smaller than 0.300, and a corresponding siloxane oligomer is obtained. May be difficult. This is presumably because, in an acidic region (pH = 4 or less) in which a cyclic siloxane bond is easily formed, hydrolysis proceeds sufficiently and many highly reactive silanol groups are present, so that a condensation reaction is likely to occur. Therefore, as described later, two or more types of siloxane oligomers having different structures may be mixed to prepare and use the siloxane oligomer (A) so as to fall within the above range.

(Synthesis of siloxane oligomer (C))
In the siloxane oligomer (A) in which two or more siloxane oligomers are mixed, at least one of the siloxane oligomers to be mixed is preferably a siloxane oligomer (C) having many cyclic siloxane bonds. In the siloxane oligomer (C), the area ratio A4 / A5 is 1.83 to 2.50, and the area ratio A6 / (A4 + A5) is 0.200 to 0.300.

  Such a siloxane oligomer (C) can be synthesized by performing condensation in a state where hydrolysis is sufficiently advanced. This is because hydrolysis proceeds sufficiently, and in the state where there are many silanol groups, condensation between silanol groups present in the vicinity tends to occur, and condensation within the siloxane oligomer molecule proceeds, resulting in cyclic siloxane bonds. This is because many generate.

  As a method for synthesizing the siloxane oligomer (C), for example, first, organosilanes and alkyl silicates which are raw materials of the siloxane oligomer (A) are mixed with alcohols. Thereafter, 0.5 mol or more of water is added to 1 mol of the total alkoxyl groups of the organosilanes and alkyl silicates, and an acid such as hydrochloric acid or acetic acid is further added to make the solution an acidic region of pH = 4 or less. Perform hydrolysis and condensation. Here, the water required for complete hydrolysis / condensation of a total of 1 mol of alkoxyl groups is 0.5 mol, and addition of 0.5 mol or more of water is sufficient for hydrolysis / condensation of alkoxyl groups. Can proceed to. The amount of water added to a total of 1 mol of alkoxyl groups is preferably 0.8 mol or more, more preferably 1 mol or more. In addition, the hydrolysis / condensation of organosilanes and alkyl silicates varies depending on the pH, and in the region of pH = 4 or less, the hydrolysis rate is faster than the condensation rate, and the hydrolysis is sufficiently performed. Can be advanced. The pH at this time is preferably pH = 3.8 or less.

  Under the present circumstances, it can also heat (for example, 30-100 degreeC), progress of reaction becomes quick, so that temperature is high, and a siloxane oligomer (C) can be obtained in a shorter time. By proceeding with condensation until the area ratio A6 / (A4 + A5) is not less than 0.200 and not more than 0.300, a siloxane oligomer having an area ratio A4 / A5 in the range of 1.83 to 2.50 (C ) Can be synthesized.

(Synthesis of siloxane oligomer (D))
Further, in the siloxane oligomer (A) obtained by mixing the two or more siloxane oligomers, the siloxane oligomer mixed with the siloxane oligomer (C) is preferably a siloxane oligomer (D) having many linear siloxane bonds. . In the siloxane oligomer (D), the area ratio A4 / A5 is 1.50 or more and less than 1.83, and the area ratio A6 / (A4 + A5) is 0.250 or more and 0.380 or less. Such a siloxane oligomer (D) can be synthesized by performing condensation in a state where hydrolysis does not proceed sufficiently. This is because hydrolysis does not proceed sufficiently, and in the state where many alkoxyl groups are present, condensation between alkoxyl groups is unlikely to occur, so condensation within the siloxane oligomer molecule is unlikely to occur and many linear siloxane bonds are formed. It is to do.

  As a method for synthesizing the siloxane oligomer (D), for example, first, organosilanes and alkyl silicates which are raw materials of the siloxane oligomer (A) are mixed with alcohols. Thereafter, hydrolysis and condensation are carried out by adding less than 0.5 mol of water to a total of 1 mol of alkoxyl groups of the organosilanes and alkyl silicates. In addition, when adding 0.5 mol or more of water, a base such as sodium hydroxide or potassium hydroxide or a salt such as sodium acetate is added to make the solution into a weakly acidic to neutral region exceeding pH = 4.・ Condensation. Here, the amount of water required to completely hydrolyze and condense a total of 1 mol of alkoxyl groups is 0.5 mol, and the amount of water added is less than 0.5 mol, so that hydrolysis and condensation are complete. Can be kept in a state of not progressing. The amount of water added to a total of 1 mol of alkoxyl groups is preferably less than 0.45 mol, and more preferably less than 0.4 mol. In addition, the hydrolysis / condensation of organosilanes and alkylsilicates varies depending on the pH, and in the region where the pH exceeds 4, the condensation rate is faster than the hydrolysis rate, and the hydrolysis is sufficient. Condensation can be carried out without progressing. The pH at this time is preferably pH = 4.8 or more.

  Under the present circumstances, it can also heat (for example, 30-100 degreeC), progress of reaction becomes quick, so that temperature is high, and a siloxane oligomer (D) can be obtained in a shorter time. By proceeding with condensation until the area ratio A6 / (A4 + A5) is not less than 0.250 and not more than 0.380, a siloxane oligomer having an area ratio A4 / A5 in the range of 1.50 or more and less than 1.83 (D ) Can be synthesized.

(Siloxane oligomer blend ratio)
As for the mixing of these siloxane oligomers, the area ratio A4 / A5 of the siloxane oligomer mixture is 1.83 or more and 2.03 or less, and the area ratio A6 / (A4 + A5) is 0.300 or more and 0.360 or less. Do as follows. The area ratio of the siloxane oligomer mixture is calculated from the area ratio and mixing ratio of the siloxane oligomer alone to be mixed. For example, siloxane oligomer X (A4 / A5 = a, A6 / (A4 + A5) = b) and siloxane oligomer Y (A4 / A5 = c, A6 / (A4 + A5) = d) are represented by X: Y = 1: m (here In the case of a siloxane oligomer mixture mixed at a mass ratio of l + m = 1), the area ratio A4 / A5 is determined as a × l + c × m, and the area ratio A6 / (A4 + A5) is determined as b × l + d × m.

  When the siloxane oligomer (A) is prepared by mixing the siloxane oligomer (C) and the siloxane oligomer (D), the area ratio A4 / A5 and the area ratio A6 / (A4 + A5) are mixed within the above ranges. Specifically, the siloxane oligomer (D) is 1 to 10000 parts by mass, preferably 10 to 1000 parts by mass, more preferably 20 to 800 parts by mass with respect to 100 parts by mass of the siloxane oligomer (C). Can be mixed.

(Active energy ray-sensitive cationic polymerization initiator (B))
The active energy ray-sensitive cationic polymerization initiator (B) used in the present invention is an initiator that causes a cationic polymerization reaction by active energy rays such as visible light, ultraviolet rays, heat rays, and electron beams. Photosensitive cationic polymerization initiators that generate acid by visible light and ultraviolet light, and heat sensitive cationic polymerization initiators that generate acid by heat rays are preferred. Among these, a photosensitive cationic polymerization initiator is more preferable because it has high activity and does not cause thermal deterioration of the plastic material.

  Examples of the photosensitive cationic polymerization initiator include diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salt compounds, and the like. Specific examples include “Irgacure 250” (trade name, manufactured by Ciba Japan Co., Ltd.), “Adekaoptomer SP-150”, “Adekaoptomer SP-170” (above, manufactured by ADEKA Corporation, trade name). ), “Syracure UVI-6970”, “Syracure UVI-6974”, “Syracure UVI-6990”, “Syracure UVI-6922”, “Syracure UVI-6950” (above, trade name, manufactured by Dow Chemical Co., Ltd.), “DAICATII” "(Trade name) manufactured by Daicel Chemical Industries, Ltd.", "UVAC1591" (trade name, manufactured by Daicel UCB), "CI-2734", "CI-2855", "CI-2823" , “CI-2758” (trade name, manufactured by Nippon Soda Co., Ltd.), “Sun Aid SI-60”, “Sun Aid SI-” 0 "," Sun-Aid SI-100 "," Sun-Aid SI-110 "," Sun-Aid SI-150 "," Sun-Aid SI-180 "(above, trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) However, it is not limited to these. Among these, a photosensitive cationic polymerization initiator whose counter ion is hexafluoroantimonate ion is preferable from the viewpoint of increasing the degree of polymerization.

  The blending amount of the active energy ray-sensitive cationic polymerization initiator (B) is not particularly limited, but is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the solid content of the siloxane oligomer (A). However, solid content means the mass part of the hydrolysis condensate produced | generated when it is assumed that the organosiloxane and alkyl silicate of siloxane oligomer (A) were completely hydrolyzed and condensed. If it is 0.01 mass part or more, it will fully harden | cure by irradiation of an active energy ray, and there exists a tendency for a favorable hard-coat layer to be obtained. If it is 10 parts by mass or less, the physical properties of the hard coat layer obtained by curing tend to be particularly low in color, and the surface hardness and scratch resistance tend to be good. Furthermore, the compounding amount is more preferably in the range of 0.05 to 5 parts by mass from the viewpoint of good curability and a hard coat layer having good performance.

  In addition, these active energy ray sensitive cationic polymerization initiators may be used alone or in combination of two or more.

(solvent)
The active energy ray-curable composition of the present invention preferably contains an organic solvent for the purpose of adjusting the solid content concentration, improving the dispersion stability, improving the coating property, and improving the adhesion to the substrate. Examples of the organic solvent include alcohols, ketones, ethers, esters, cellosolves, aromatic compounds, and the like.

  Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxy Methoxy) ethanol, 2-butoxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diacetone alcohol, Seton, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, acetophenone, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , Dihexyl ether, anisole, phenetole, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, glycerin ether, Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoacetic acid Chill, sec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, butyl propionate, γ-butyrolactone, 2-methoxyethyl Examples include, but are not limited to, acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzene, toluene, xylene and the like. . These organic solvents may be used alone or in combination of two or more.

(Silicon hard coat layer formation method)
Next, a method for forming a silicon hard coat layer in the present invention will be described.

  The silicon-based hard coat layer in the present invention is based on an active energy ray-curable coating composition mainly composed of a siloxane oligomer (A) having a specific structure and an active energy ray-sensitive cationic polymerization initiator (B). It is applied to the surface of the material and formed by irradiating with active energy rays and crosslinking and curing.

  The application of the active energy ray curable composition is conventionally known methods, for example, bar coating method, spray coating method, roll coating method, gravure coating method, flexo coating method, screen method, spin coating method, flow coating method, It can be performed by an electrostatic coating method or the like.

  As a film thickness of the film formed by application | coating of an active energy ray curable composition, 5-200 micrometers is preferable from the point which can improve abrasion resistance and crack resistance more.

  Examples of the active energy rays include vacuum ultraviolet rays, ultraviolet rays, visible rays, near infrared rays, infrared rays, far infrared rays, microwaves, electron beams, β rays, and γ rays. Among them, it is possible to use ultraviolet light and visible light in combination with a photosensitive cationic polymerization initiator whose counter ion is hexafluoroantimonate ion because the polymerization rate is fast and the deterioration of the substrate is relatively small. preferable.

  Specific examples include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, incandescent bulbs, xenon lamps, halogen lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, gallium lamps, excimer lasers, and the sun. An active energy ray as a light source can be mentioned. One type of active energy ray may be used alone, or a plurality of different types may be used. When different types of active energy rays are used, they may be irradiated simultaneously or sequentially.

  Furthermore, from the viewpoint of improving the curing efficiency of the film by irradiation with active energy rays, it is preferable to use both irradiation with active energy rays and heating the coating to a specific temperature range. The optimum coating temperature for heating the coating is 60 ° C to 90 ° C. When the coating temperature is 60 ° C. or higher, curing of the coating by irradiation with active energy rays can be effectively promoted. Moreover, in the case of 90 degrees C or less, hardening can be accelerated | stimulated, suppressing generation | occurrence | production of the crack by the stress which generate | occur | produces with rapid hardening shrinkage | contraction, and the fall of base-material adhesiveness. Moreover, when the heat-resistant temperature of a base material is lower than the said temperature, it is preferable to set it as less than the heat-resistant temperature of a base material.

  The method for heating the coating to a specific temperature range is not particularly limited, and for example, a hot air furnace, an electric furnace, a steam drying furnace, infrared irradiation, induction heating, or the like can be used. The step of heating the coating to a specific temperature can be performed before, during, or after irradiation of the active energy ray. You may heat-retain using a heat insulating material etc. so that the film temperature at the time of irradiating a line may not deviate from a specific temperature range by natural cooling.

  Thereby, the hard coat molded article which has a silicon-type hard-coat layer on the surface of the base material which concerns on this invention is obtained. In addition, it is preferable that the film thickness of this silicon-type hard-coat layer is 0.5-100 micrometers from the point which can improve abrasion resistance and crack resistance more.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In the following description, “part” means “part by mass”.

<Synthesis Example 1: Synthesis of Siloxane Oligomer (C1)>
As organosilanes, methyltrimethoxysilane (manufactured by Tama Chemical Co., Ltd., molecular weight 136) 126.48 parts (93 mol%), phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 198) 13.86 parts (7 Mol%) was added with 108.28 parts of isopropyl alcohol and stirred to obtain a uniform solution. Furthermore, 107.76 parts of water and 0.24 part of a 1 mol / L hydrochloric acid aqueous solution were added, and the mixture was heated at 80 ° C. for 3 hours with stirring to perform hydrolysis and condensation. At this time, the molar ratio of the alkoxyl group to water was alkoxyl group / water = 1/2, and the pH of the solution was 3.5. Thereafter, the mixture was cooled to 25 ° C. and stirred for 24 hours to allow condensation to proceed to obtain 356.62 parts of a siloxane oligomer (C1) solution having a solid concentration of 20% by mass.

About the obtained siloxane oligomer (C1), an appropriate amount is dropped on an acrylic plate (trade name: “Acrylite EX”, manufactured by Mitsubishi Rayon Co., Ltd.) having a length of 10 cm, a width of 10 cm, and a thickness of 3 mm, and a bar coating method (bar coater). No. 28) and the solvent was dried at room temperature. Thereafter, infrared absorption measurement was performed by the ATR method using FT-IR (trade name: “NEXUS470”, manufactured by Thermo Nicolet Co., Ltd.). As measurement conditions, an ATR measurement accessory (trade name “FOUNDATION ThunderDome”, manufactured by Spectratech) was attached, and the measurement was performed with a resolution of 4 cm ⁻¹ and 32 integrations. Moreover, the peak area was calculated | required using the integration tool of FT-IR analysis software (Brand name "OMNIC", the product made by Thermo Nicolet Co., Ltd.).

  As a result, the area ratio A4 / A5 of the peak area A4 of the infrared absorption spectrum caused by the cyclic siloxane bond of the siloxane oligomer (C1) and A5 of the infrared absorption spectrum caused by the linear siloxane bond was 2.17. . Further, the ratio A6 / (A4 + A5) between the sum of absorption caused by the siloxane bond (A4 + A5) and the peak area A6 of the infrared absorption spectrum caused by the silanol group was 0.299. The results are shown in Table 1.

<Synthesis Example 2: Synthesis of Siloxane Oligomer (D1)>
A solution of siloxane oligomer (D1) having a solid content concentration of 20% by mass, as in Synthesis Example 1, except that 0.24 part of 1 mol / L hydrochloric acid aqueous solution was not added and the amount of water added was 108.00 parts. 62 parts were obtained. In this case, the pH of the solution was 4.8. The peak area ratio A4 / A5 of the infrared absorption spectrum of the obtained siloxane oligomer (D1) was 1.75, and the peak area ratio A6 / (A4 + A5) was 0.345. The results are shown in Table 1.

<Synthesis Example 3: Synthesis of Siloxane Oligomer (C2)>
As organosilanes, methyltrimethoxysilane (manufactured by Tama Chemical Co., Ltd., molecular weight 136) 122.40 parts (90 mol%), phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 198) 13.86 parts (7 Mol.%), 105.67 parts of isopropyl alcohol was added to 4.56 parts (3 mol%) of tetramethoxysilane (manufactured by Tama Chemical Co., Ltd., molecular weight 152) as alkyl silicates, and stirred to obtain a uniform solution. . Further, 108.84 parts of water and 0.24 part of a 1 mol / L hydrochloric acid aqueous solution were added, and the mixture was heated at 80 ° C. for 3 hours with stirring to perform hydrolysis and condensation. At this time, the molar ratio of alkoxyl group to water was alkoxyl group / water = 1/2, and the pH of the solution was 3.6. Thereafter, the mixture was cooled to 25 ° C. and stirred for 24 hours to proceed with condensation to obtain 355.57 parts of a siloxane oligomer (C2) solution having a solid concentration of 20% by mass. The peak area ratio A4 / A5 of the infrared absorption spectrum of the obtained siloxane oligomer (C2) was 2.23, and the peak area ratio A6 / (A4 + A5) was 0.281. The results are shown in Table 1.

<Synthesis Example 4: Synthesis of Siloxane Oligomer (D2)>
A solution of siloxane oligomer (D2) having a solid content concentration of 20% by mass, as in Synthesis Example 3, except that 0.24 part of 1 mol / L hydrochloric acid aqueous solution was not added and the amount of water added was 109.08 parts. 57 parts were obtained. In this case, the pH of the solution was 4.8. The peak area ratio A4 / A5 of the infrared absorption spectrum of the obtained siloxane oligomer (D2) was 1.77, and the peak area ratio A6 / (A4 + A5) was 0.322. The results are shown in Table 1.

<Example 1>
[Preparation of active energy ray-curable composition]
10.0 parts (solid content 2.0 parts) of a 20% by mass solid content concentration of the siloxane oligomer (C1) obtained in Synthesis Example 1 as the component (C) and the siloxane obtained in Synthesis Example 2 as the component (D) 40.0 parts (solid content 8.0 parts) of 20% by weight solid content concentration of oligomer (D1) were mixed to obtain 50.0 parts (A) siloxane oligomer mixture (solid content 10.0 parts). . For this (A) siloxane oligomer mixture, the peak area ratio A4 / A5 of the infrared absorption spectrum calculated from the area ratio and mixing ratio of each siloxane oligomer alone is 1.83, and the area ratio A6 / (A4 + A5) is 0.336. Met. To this (A) siloxane oligomer mixture, as component (B), “Sun Aid SI-80L” (manufactured by Sanshin Chemical Industry Co., Ltd., sulfonium salt-based photosensitive cationic polymerization initiator, solid concentration 50 mass% γ- Butyrolactone solution (trade name) 0.2 part (solid content 0.1 part) was blended. Furthermore, 10.0 parts of isopropyl alcohol, 15.0 parts of γ-butyrolactone, 10.0 parts of butyl cellosolve as a solvent, and a silicone surfactant as a leveling agent (trade name: “L-7001”, manufactured by Toray Dow Corning Co., Ltd.) 0.01 part was mixed and the active energy ray curable composition was obtained.

[Formation of film]
An appropriate amount of this active energy ray-curable composition is dropped on an acrylic plate (trade name: “Acrylite EX”, manufactured by Mitsubishi Rayon Co., Ltd.) having a length of 10 cm, a width of 10 cm, and a thickness of 3 mm, and a bar coating method (bar coater). No. 28 use). This was heated in a dryer at 90 ° C. for 10 minutes.

[Curing of coating]
The film temperature after the heating was measured with a radiation thermometer (trade name: “IT-311”, manufactured by ASONE CORPORATION). With the coating temperature at 90 ° C., the belt conveyor type high-pressure mercury lamp (Oak Manufacturing Co., Ltd., ultraviolet irradiation device, trade name: “Handy UV-1200, QRU-2161”) quickly while the coating has not cooled. The sample was irradiated with ultraviolet rays of about 1,000 mJ / cm ² . As a result, a hard coat molded article having a silicon hard coat layer was obtained. The amount of ultraviolet irradiation was measured with an ultraviolet light meter (trade name: “UV-351 type”, manufactured by Oak Manufacturing Co., Ltd., peak sensitivity wavelength 360 nm). The coating temperature immediately after irradiation was 76 ° C.

[Evaluation of hard coat layer]
The obtained hard coat layer was evaluated by the following methods.

1) Infrared absorption measurement Infrared absorption measurement of the hard coat layer was performed by the ATR method by FT-IR (trade name: “NEXUS470”, manufactured by Thermo Nicolet). As measurement conditions, an ATR measurement accessory (trade name “FOUNDATION ThunderDome”, manufactured by Spectratech) was attached, and the measurement was performed with a resolution of 4 cm ⁻¹ and 32 integrations. Moreover, the peak area was calculated | required using the integration tool of FT-IR analysis software (Brand name "OMNIC", the product made from a Thermo Nicolet company). From the obtained infrared absorption spectrum, the peak area ratio A1 / A2 and the peak area ratio A3 / (A1 + A2) were determined.

2) Appearance The transparency, crack resistance, and whitening of the acrylic plate having the hard coat layer were visually observed and evaluated according to the following criteria.
“◯”: Transparent and free from defects such as cracks and whitening (good).
“X”: An opaque part, a defect such as a crack or whitening (defect).

3) Film thickness The cross section of the acrylic board which has a hard-coat layer was observed with the scanning electron microscope, and the film thickness of the hard-coat layer was measured.

4) Adhesiveness of base material 11 pieces of vertical and horizontal cuts were made at intervals of 1 mm with a razor blade on the hard coat layer on the surface of the acrylic plate to make 100 squares, and the cellophane tape was well adhered. Then, it peeled off rapidly 45 degree | times, and the number of squares which the hard-coat layer remained without peeling was measured, and the following references | standards evaluated.
“◯”: There is no peeled cell (good adhesion).
“Δ”: 1 to 5 peeled squares (medium adhesion).
"X": Six or more squares which peeled (adhesion failure).

5) Scratch resistance The surface of the acrylic board having the hard coat layer was rubbed 10 times with # 0000 steel wool by applying a pressure of 9.8 × 10 ⁴ Pa, and the degree of scratches generated in the range of 1 cm × 3 cm was determined. Observed and evaluated according to the following criteria.
“A”: There is no scratch.
“B”: 1 to 9 scratches are attached. There is a glossy surface.
“C +”: 10 to 49 scratches are attached. There is a glossy surface.
"C-": 50 to 99 scratches are attached. There is a glossy surface.
"D": 100 or more scratches are attached. There is a glossy surface.
“E”: The glossy surface disappears.

6) Crack resistance The hard coat layer coated on the acrylic plate was left standing for a certain period in an environment of a temperature of 25 ° C. and a humidity of 50%, and the occurrence of cracks was visually confirmed.
“O”: No cracks occurred for more than 3 months.
“△”: No cracks occurred in 1 week, but cracks were confirmed after 3 months.
“×”: Crack occurred in one week.

  The infrared absorption spectrum of the hard coat layer obtained in Example 1 is shown in FIG. As a result of the above evaluation, the hard coat layer according to the present example is a value in which the area ratio A1 / A2 and the area ratio A3 / (A1 + A2) are in the optimum range, and has good appearance, substrate adhesion, resistance It had scratch resistance and crack resistance. The results are shown in Table 2.

<Example 2>
As component (C), 30.0 parts (solid content 6.0 parts) of a 20% by mass solid content concentration of the siloxane oligomer (C1) obtained in Synthesis Example 1 and as component (D), the siloxane oligomer obtained in Synthesis Example 2 50.0 parts (solid content 10.0 parts) of (A) siloxane oligomer mixed with 20.0 parts (solid content 4.0 parts) of a solid content concentration 20 mass% solution of (D1) was used. Other than that was carried out similarly to Example 1, and prepared active energy ray-curable composition, formation and hardening of a film, and evaluation of the hard-coat layer. The results are shown in Table 2.

<Example 3>
10.0 parts (solid content 2.0 parts) of a 20% by mass solid content concentration of the siloxane oligomer (C2) obtained in Synthesis Example 3 as the component (C), and the siloxane oligomer obtained in Synthesis Example 4 as the component (D) 50.0 parts (solid content 10.0 parts) of (A) siloxane oligomer mixed with 40.0 parts (solid content 8.0 parts) of a solid content concentration 20% by mass solution of (D2) was used. Other than that was carried out similarly to Example 1, and prepared active energy ray-curable composition, formation and hardening of a film, and evaluation of the hard-coat layer. The results are shown in Table 2.

<Example 4>
(C) 25.0 parts (solid content 5.0 parts) of a 20% by weight solid content concentration of the siloxane oligomer (C2) obtained in Synthesis Example 3 as the component, and (siloxane) oligomer obtained in Synthesis Example 4 as the component (D) 50.0 parts (solid content 10.0 parts) of (A) siloxane oligomer mixed with 25.0 parts (solid content 5.0 parts) of a solid content concentration 20 mass% solution of (D2) was used. Other than that was carried out similarly to Example 1, and prepared active energy ray-curable composition, formation and hardening of a film, and evaluation of the hard-coat layer. The results are shown in Table 2.

<Comparative Example 1>
As component (A), 50.0 parts (solid content 5.0 parts) of a 20% by mass solid content concentration of the siloxane oligomer (C1) obtained in Synthesis Example 1 was used, and component (D) was not mixed. Other than that was carried out similarly to Example 1, and prepared active energy ray-curable composition, formation and hardening of a film, and evaluation of the hard-coat layer.

  The infrared absorption spectrum of the hard coat layer obtained in Comparative Example 1 is shown in FIG. (A) The area ratio A4 / A5 of the siloxane oligomer is large. As a result, the area ratio A1 / A2 of the hard coat layer is also large, and the amount of cyclic siloxane bonds contained is large, so that the scratch resistance is higher than that of Example 1. It was inferior. The results are shown in Table 3.

<Comparative example 2>
As component (A), 50.0 parts (solid content 5.0 parts) of a 20% by weight solid content concentration of the siloxane oligomer (D1) obtained in Synthesis Example 2 was used, and component (C) was not mixed. Other than that was carried out similarly to Example 1, and prepared active energy ray-curable composition, formation and hardening of a film, and evaluation of the hard-coat layer.

  The infrared absorption spectrum of the hard coat layer obtained in Comparative Example 2 is shown in FIG. (A) The area ratio A4 / A5 of the siloxane oligomer is small. As a result, the area ratio A1 / A2 of the hard coat layer is also small, and the amount of cyclic siloxane bonds contained is small. It was inferior. The results are shown in Table 3.

<Comparative Example 3>
The component (C) is a siloxane oligomer (C1) obtained in Synthesis Example 1 having a solid content concentration of 20 parts by mass of 5.0 parts (solid content: 1.0 part), and the component (D) is a siloxane oligomer obtained in Synthesis Example 2. 50.0 parts (solid content 10.0 parts) of (A) siloxane oligomer mixed with 45.0 parts (solid content 9.0 parts) of a solid content concentration 20% by mass solution of (D1) was used. Other than that was carried out similarly to Example 1, and prepared active energy ray-curable composition, formation and hardening of a film, and evaluation of the hard-coat layer.

  (A) The area ratio A4 / A5 of the siloxane oligomer mixture is small. As a result, the area ratio A1 / A2 of the hard coat layer is also small, and the amount of cyclic siloxane bonds contained is small. It was inferior. The results are shown in Table 3.

<Comparative example 4>
(C) 35.0 parts (solid content 7.0 parts) of a 20% by weight solid content concentration of the siloxane oligomer (C1) obtained in Synthesis Example 1 as the component, and (siloxane) oligomer obtained in Synthesis Example 2 as the component (D) 50.0 parts (solid content 10.0 parts) of (A) siloxane oligomer mixed with 15.0 parts (solid content 3.0 parts) of a solid content concentration 20 mass% solution of (D1) was used. Other than that was carried out similarly to Example 1, and prepared active energy ray-curable composition, formation and hardening of a film, and evaluation of the hard-coat layer.

  (A) The area ratio A4 / A5 of the siloxane oligomer mixture is large. As a result, the area ratio A1 / A2 of the hard coat layer is also large, and the amount of cyclic siloxane bonds contained is large, so the scratch resistance is higher than that of Example 1. It was inferior. The results are shown in Table 3.

<Comparative Example 5>
The component (C) is a siloxane oligomer (C2) obtained in Synthesis Example 3 having a solid content concentration of 20 parts by mass of 5.0 parts (solid content: 1.0 part), and the component (D) is a siloxane oligomer obtained in Synthesis Example 4. 50.0 parts (solid content 10.0 parts) of (A) siloxane oligomer mixed with 45.0 parts (solid content 9.0 parts) of a solid content concentration 20% by mass solution of (D2) was used. Other than that was carried out similarly to Example 3, and preparation of the active energy ray hardening composition, formation and hardening of a film, and evaluation of the hard-coat layer were implemented.

  (A) The area ratio A4 / A5 of the siloxane oligomer mixture is small. As a result, the area ratio A1 / A2 of the hard coat layer is also small, and the amount of cyclic siloxane bonds contained is small. It was inferior. The results are shown in Table 3.

<Comparative Example 6>
As component (C), 30.0 parts (solid content 6.0 parts) of a 20% by weight solid content concentration of the siloxane oligomer (C2) obtained in Synthesis Example 3 as a component, and the siloxane oligomer obtained in Synthesis Example 4 as a component (D). 50.0 parts (solid content 10.0 parts) of (A) siloxane oligomer mixed with 20.0 parts (solid content 4.0 parts) of a solid content concentration 20% by mass solution of (D2) was used. Other than that was carried out similarly to Example 3, and preparation of the active energy ray hardening composition, formation and hardening of a film, and evaluation of the hard-coat layer were implemented.

  (A) The area ratio A4 / A5 of the siloxane oligomer mixture is large. As a result, the area ratio A1 / A2 of the hard coat layer is also large, and the amount of cyclic siloxane bonds contained is large. It was inferior. The results are shown in Table 3.

As is clear from Tables 2 and 3 below, the hard coat layers of the examples have better scratch resistance and crack resistance than those of the comparative examples, and also have good appearance and substrate adhesion. Met.

Infrared absorption spectrum of the absorbance C silicon-based hard coat layer point indicating the at 960 cm ^-1 in the infrared absorption spectrum of the point B silicon-based hard coat layer exhibiting absorbance at 1240 cm ^-1 in the infrared absorption spectrum of A silicon-based hard coat layer F siloxane point indicating the absorbance at 1240 cm ^-1 in the infrared absorption spectrum of the E siloxane oligomer that shows the absorbance at 860 cm ^-1 in the infrared absorption spectrum of the point D silicon-based hard coat layer at 1050 cm ^-1 on the line segment AB in 8 in the infrared absorption spectrum of the point H siloxane oligomers in 1050 cm ^-1 on the line segment EF in the infrared absorption spectrum of the G siloxane oligomer that shows the absorbance at 960 cm ^-1 in the infrared absorption spectrum of the oligomer Infrared absorption peak area of the spectrum due to the straight-chain siloxane bond infrared absorption peak area A2 silicon-based hard coat layer of the spectrum due to the cyclic siloxane bond absorbance A1 silicon-based hard coat layer point indicating the at 0 cm ^-1 A3 Infrared absorption peak area of spectrum caused by silanol group of silicon hard coat layer A4 Infrared absorption peak area of spectrum caused by cyclic siloxane bond of siloxane oligomer A5 Infrared absorption peak of spectrum caused by linear siloxane bond of siloxane oligomer Area A6 Infrared absorption peak area of spectrum caused by silanol group of siloxane oligomer

Claims (7)

A molded product having a silicon-based hard coat layer cured by active energy rays on the surface of the substrate,
The area ratio A1 / A2 between the peak area A1 of the infrared absorption spectrum caused by the cyclic siloxane bond of the silicon-based hard coat layer and the peak area A2 of the infrared absorption spectrum caused by the linear siloxane bond is 0.83 or more, 0 The ratio A3 / (A1 + A2) between the sum of A1 and A2 (A1 + A2) and the peak area A3 of the infrared absorption spectrum caused by the silanol group is 0.020 or more and 0.028 or less. Code molded product. (A) The area ratio A4 / A5 between the peak area A4 of the infrared absorption spectrum caused by the cyclic siloxane bond and the peak area A5 of the infrared absorption spectrum caused by the linear siloxane bond is 1.83 or more and 2.03 or less. A siloxane oligomer having an area ratio A6 / (A4 + A5) of 0.300 or more and 0.360 or less between the sum of A4 and A5 (A4 + A5) and the peak area A6 of the infrared absorption spectrum caused by the silanol group;
The active energy ray-curable cationic polymerization initiator containing (B) an active energy ray-sensitive cationic polymerization initiator is applied to the surface of the base material, and the active energy ray is irradiated and crosslinked and cured. Manufacturing method of hard coat molded product. The (A) siloxane oligomer is
(C) a siloxane oligomer in which the area ratio A4 / A5 is 1.83 or more and 2.50 or less, and the area ratio A6 / (A4 + A5) is 0.200 or more and 0.300 or less;
(D) a mixture of the area ratio A4 / A5 is 1.50 or more and less than 1.83, and the area ratio A6 / (A4 + A5) is 0.250 or more and 0.380 or less. The manufacturing method of the hard coat molded article of a certain 2 item | term. (A) The area ratio A4 / A5 between the peak area A4 of the infrared absorption spectrum caused by the cyclic siloxane bond and the peak area A5 of the infrared absorption spectrum caused by the linear siloxane bond is 1.83 or more and 2.03 or less. A siloxane oligomer having an area ratio A6 / (A4 + A5) of 0.300 or more and 0.360 or less between the sum of A4 and A5 (A4 + A5) and the peak area A6 of the infrared absorption spectrum caused by the silanol group;
(B) An active energy ray-curable coating composition containing an active energy ray-sensitive cationic polymerization initiator. The (A) siloxane oligomer is
(C) a siloxane oligomer in which the area ratio A4 / A5 is 1.83 or more and 2.50 or less, and the area ratio A6 / (A4 + A5) is 0.200 or more and 0.300 or less;
(D) a mixture of the area ratio A4 / A5 is 1.50 or more and less than 1.83, and the area ratio A6 / (A4 + A5) is 0.250 or more and 0.380 or less. The active energy ray-curable coating composition according to claim 4. (C) The area ratio A4 / A5 between the peak area A4 of the infrared absorption spectrum caused by the cyclic siloxane bond and the peak area A5 of the infrared absorption spectrum caused by the linear siloxane bond is 1.83 or more and 2.50 or less. A siloxane oligomer having an area ratio A6 / (A4 + A5) of 0.200 or more and 0.300 or less between the sum of A4 and A5 (A4 + A5) and the peak area A6 of the infrared absorption spectrum caused by the silanol group;
(D) a siloxane oligomer in which the area ratio A4 / A5 is 1.50 or more and less than 1.83, and the area ratio A6 / (A4 + A5) is 0.250 or more and 0.380 or less;
The active energy ray-curable cationic polymerization initiator containing (B) an active energy ray-sensitive cationic polymerization initiator is applied to the surface of the base material, and the active energy ray is irradiated and crosslinked and cured. Manufacturing method of hard coat molded product. (C) The area ratio A4 / A5 between the peak area A4 of the infrared absorption spectrum caused by the cyclic siloxane bond and the peak area A5 of the infrared absorption spectrum caused by the linear siloxane bond is 1.83 or more and 2.50 or less. A siloxane oligomer having an area ratio A6 / (A4 + A5) of 0.200 or more and 0.300 or less between the sum of A4 and A5 (A4 + A5) and the peak area A6 of the infrared absorption spectrum caused by the silanol group;
(D) a siloxane oligomer in which the area ratio A4 / A5 is 1.50 or more and less than 1.83, and the area ratio A6 / (A4 + A5) is 0.250 or more and 0.380 or less;
(B) An active energy ray-curable coating composition containing an active energy ray-sensitive cationic polymerization initiator.

Images