JP2016016338A - Method of manufacturing resin substrate with hard coat layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method allowing for improvement in productivity of a resin substrate with a hard coat layer and also allowing for increase in flexibility of selection of substrate material.SOLUTION: A method of manufacturing a resin substrate with a hard coat layer, which has the hard coat layer on at least one surface of the resin substrate is provided. The method comprises: a step of applying a hard coat agent composition which contains organopolysiloxane and a UV light absorption agent having the absorbance at wavelength 220 nm measured on conditions of optical path length 1 cm with respect to an acetonitrile solution of concentration of 0.001 mass%, of 0.2 or more, onto at least one surface of the resin substrate thereby forming a coating film made of the hard coat agent composition and, thereafter, subjecting the coating film to Xeexcimer light irradiation under a low oxygen environment thereby forming a cured film; and a step of oxidizing the cured film and, thereafter, subjecting the oxidized cured film to heat treatment thereby forming the hard coat layer.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a resin substrate with a hard coat layer.

  In recent years, the demand for transparent resin plates in place of inorganic glass plates has been increasing as window materials for vehicles such as automobiles and window materials for building materials attached to buildings such as houses and buildings. In particular, in vehicles such as automobiles, it has been proposed to use a transparent resin plate for the window material in order to reduce the weight. In particular, an aromatic polycarbonate-based transparent resin plate is resistant to breakage, transparency, lightness, and ease. Since it is excellent in workability and the like, its use is considered as a promising vehicle window material. However, such a transparent resin plate has a problem in terms of scratch resistance when used instead of a glass plate.

  Therefore, for the purpose of improving the scratch resistance of the transparent resin plate, it has been proposed to form a high-hardness coating (hard coat layer) on the surface of the transparent resin plate using various hard coat agents. At that time, it has also been proposed to provide a primer layer on the transparent resin plate in order to improve the adhesion between the transparent resin plate and the hard coat layer.

  By the way, in order to form a high-hardness film, generally, a composition based on an organopolysiloxane that cures by a condensation reaction of a silanol group is used for the hard coating agent. The hard coat layer is then heated for about 1 hour at a temperature of about 120 ° C. in order to cure the coating film after applying such a composition on the transparent resin plate or the transparent resin plate on which the primer layer is formed. Or after that, the coating film is further irradiated with light (see, for example, Patent Document 1).

  However, such a conventional hard coat agent and hard coat layer forming method requires a heat treatment of about 1 hour at a temperature of about 120 ° C. for curing the coating film, and is difficult to apply to a continuous coating process. There was a problem that productivity could not be improved. Moreover, since the transparent resin plate of the base material must be able to withstand such a heat treatment, there is a problem that the material is limited.

International Publication No. 2009-110152

  The present invention has been made in response to the above-described problems of the prior art, and can improve the productivity of a resin substrate with a hard coat layer in which a hard coat layer having sufficient scratch resistance is formed on the resin substrate. An object of the present invention is to provide a method for producing a resin substrate with a hard coat layer, which can increase the degree of freedom in selecting a substrate material.

One embodiment of the present invention is a method for producing a resin substrate with a hard coat layer, which has a hard coat layer on at least one surface of the resin substrate, and includes an organopolysiloxane and an acetonitrile solution having a concentration of 0.001% by mass. A coating film comprising the composition obtained by applying a hard coat agent composition containing an ultraviolet absorber having an absorbance of 0.2 or more at a wavelength of 220 nm measured under an optical path length of 1 cm on at least one surface of the resin substrate. Forming a cured film by subjecting the coating film to a Xe ₂ excimer light irradiation treatment in a low oxygen atmosphere, and a step of oxidizing the cured film and then subjecting it to a heat treatment to form a hard coat layer It is characterized by comprising.

  Here, the “cured film” used in the present specification refers to a cured film obtained by condensation-curing a hard coating agent composition containing an organopolysiloxane in the form of a coating film with light as described later. “Hard coat layer” refers to the final form of a film provided on a resin substrate for surface protection. Generally, the cured film may be used as it is as a hard coat layer. In the layer, a surface protective film obtained by further subjecting the cured film to surface treatment (oxidation treatment / heat treatment) is a hard coat layer.

  ADVANTAGE OF THE INVENTION According to this invention, while being able to improve the productivity of the resin substrate with a hard-coat layer in which the hard-coat layer which has sufficient abrasion resistance was formed on the resin substrate, the freedom degree of the selection of the material used for a board | substrate was improved. Can be increased.

Embodiments of the present invention will be described below.
<The manufacturing method of the resin substrate with a hard-coat layer of this invention>
The resin substrate with a hard coat layer targeted by the production method of the present invention has a hard coat layer on at least one surface of the resin substrate. In this specification, “having a hard coat layer on the surface of the resin substrate” means a primer layer described later on the surface of the resin substrate in addition to the case of having the hard coat layer directly on the surface of the resin substrate. The case where a hard coat layer is provided via a functional layer as described above is also included. That is, the manufacturing method of the present invention can be applied to a resin substrate with a hard coat layer in which a functional layer such as a primer layer and a hard coat layer are sequentially laminated on the resin substrate.

  In the production of such a resin substrate with a hard coat layer, the production method of the present invention includes the following (1) a step of forming a cured film of a hard coat agent composition containing an organopolysiloxane and an ultraviolet absorber (hereinafter referred to as “a hard coat layer”). And “(2) oxidation treatment / heat treatment step”.

(1) Cured film forming step The cured film forming step in the production method of the present invention is carried out by applying a hard coat agent composition containing an organopolysiloxane and an ultraviolet absorber on at least one surface of a resin substrate. After forming the coating film, the obtained coating film is subjected to Xe ₂ excimer light irradiation treatment to form a cured film.

(1-1) Resin Substrate As a resin constituting the resin substrate used in the present invention, polycarbonate resin, polystyrene resin, aromatic polyester resin, acrylic resin, polyester resin, polyarylate resin, halogenated bisphenol A and ethylene glycol are used. Examples include polycondensates, acrylic urethane resins, and halogenated aryl group-containing acrylic resins.

  Among these, polycarbonate resins such as aromatic polycarbonate resins and acrylic resins such as polymethyl methacrylate acrylic resins are preferable, and polycarbonate resins are more preferable. Furthermore, bisphenol A-based polycarbonate resin is particularly preferable among polycarbonate resins. The resin substrate may contain two or more types of thermoplastic resins as described above, or may be a laminated substrate in which two or more layers are laminated using these resins. The shape of the resin substrate is not particularly limited, and may be a flat plate or curved. Furthermore, the color tone of the resin substrate is preferably colorless and transparent or colored and transparent.

(1-2) Preparation of hard coat agent composition The hard coat agent composition used in the production method of the present invention contains an organopolysiloxane and an ultraviolet absorber as essential components, and is further optionally added as necessary. In a range not impairing the effects of the present invention. Hereinafter, each component contained in the hard coat agent composition will be described.

(Organopolysiloxane)
The organopolysiloxane contained in the hard coat agent composition used in the production method of the present invention can be used without particular limitation as long as it is a curable organopolysiloxane.

Organopolysiloxane is composed of silicon-containing bond units called M units, D units, T units, and Q units. Among these, curable organopolysiloxane is an oligomeric polymer mainly composed of T units or Q units, a polymer composed only of T units, a polymer composed only of Q units, T units and Q units. There is a polymer composed of These polymers may further contain a small amount of M units and D units.

In the curable organopolysiloxane, the T unit has one silicon atom, one hydrogen atom or monovalent organic group bonded to the silicon atom, and an oxygen atom bonded to another silicon atom ( Or a unit having three functional groups capable of bonding to other silicon atoms). The monovalent organic group bonded to the silicon atom is a monovalent organic group in which the atom bonded to the silicon atom is a carbon atom. The functional group that can be bonded to another silicon atom is a hydroxyl group or a group that becomes a hydroxyl group by hydrolysis (hereinafter referred to as a hydrolyzable group). The total number of oxygen atoms bonded to other silicon atoms and functional groups that can bond to other silicon atoms is three, and the number of functional groups that can bond to oxygen atoms bonded to other silicon atoms and other silicon atoms is different. Thus, the T unit is classified into three types of units called T1, T2, and T3. T1 has one oxygen atom bonded to another silicon atom, T2 has two oxygen atoms, and T3 has three oxygen atoms. In this specification and the like, an oxygen atom bonded to another silicon atom is represented by O ^* , and a monovalent functional group that can be bonded to another silicon atom is represented by Z.

Note that O ^* representing an oxygen atom bonded to another silicon atom is an oxygen atom bonded between two silicon atoms, and is an oxygen atom in a bond represented by Si-O-Si. Accordingly, one O ^* exists between the silicon atoms of two silicon-containing bond units. In other words, O ^* represents an oxygen atom shared by two silicon atoms of two silicon-containing bond units. In the chemical formula of the silicon-containing bond unit described later, it is expressed as O ^* is bonded to one silicon atom, but this O ^* is an oxygen atom shared with the silicon atom of another silicon-containing bond unit. It does not mean that two silicon-containing bond units are bonded by a bond represented by Si—O ^* —O ^* —Si.

The M unit is a unit having 3 organic groups and 1 O ^* , the D unit is a unit having 2 organic groups and 2 O ^* (or 1 O ^{* and} 1 Z group), and the Q unit is It is a unit having 0 organic groups and 4 O ^* (or 4 O ^* 1 to 3 and 3 to 3 Z groups). Each silicon-containing bond unit is formed from a compound (hereinafter also referred to as a monomer) that does not have an oxygen atom (O ^* ) bonded to another silicon atom (has only a Z group). The monomer forming the T unit is hereinafter referred to as T monomer. Monomers that form M units, D units, and Q units are also referred to as M monomers, D monomers, and Q monomers.

The monomer is represented by (R′—) _a Si (—Z) _4-a . However, a represents an integer of 0 to 3, R ′ represents a hydrogen atom or a monovalent organic group, and Z represents a monovalent functional group that can be bonded to a hydroxyl group or another silicon atom. In this chemical formula, a compound with a = 3 is an M monomer, a compound with a = 2 is a D monomer, a compound with a = 1 is a T monomer, and a compound with a = 0 is a Q monomer. In the monomer, the Z group is usually a hydrolyzable group. Further, when 2 or 3 R ′ are present (when a is 2 or 3), the plurality of R ′ may be different. R ′ is preferably in the same category as R described later.

The curable organopolysiloxane is obtained by a reaction in which a part of the Z group of the monomer is converted to O ^* . When the organopolysiloxane is a copolymer comprising two or more silicon-containing bond units, these copolymers are usually obtained from a mixture of the corresponding monomers. When the Z group of the monomer is a hydrolyzable group, the Z group is converted into a hydroxyl group by a hydrolysis reaction, and then two silicon atoms are converted by a dehydration condensation reaction between two hydroxyl groups bonded to separate silicon atoms. Bonding through an oxygen atom (O ^* ). In the curable organopolysiloxane, hydroxyl groups (or Z groups that have not been hydrolyzed) remain, and when the curable organopolysiloxane is cured, these hydroxyl groups and Z groups react and cure as described above. The cured product of the curable organopolysiloxane is a three-dimensionally crosslinked polymer, and the cured product of the curable organopolysiloxane having many T units and Q units is a cured product having a high crosslinking density. At the time of curing, the Z group of the curable organopolysiloxane is converted to O ^* , but a part of the Z group (particularly hydroxyl group) remains and is considered to be a cured product having a hydroxyl group. When the curable organopolysiloxane is cured at a high temperature, it may be a cured product in which almost no hydroxyl groups remain.

  When the Z group of the monomer is a hydrolyzable group, examples of the Z group include an alkoxy group, a chlorine atom, an acyloxy group, and an isocyanate group. In many cases, a monomer in which the Z group is an alkoxy group is used as the monomer. The alkoxy group is a hydrolyzable group having a relatively low reactivity as compared with a chlorine atom and the like, and in the curable organopolysiloxane obtained by using a monomer in which the Z group is an alkoxy group, it is not present together with the hydroxyl group as a Z group. Often an alkoxy group of the reaction is present. When the Z group of the monomer is a hydrolyzable group having a relatively high reactivity (for example, a chlorine atom), most of the Z groups in the curable organopolysiloxane obtained using the monomer are hydroxyl groups. Therefore, in a normal curable organopolysiloxane, the Z group in each unit constituting it is often composed of a hydroxyl group or a hydroxyl group and an alkoxy group.

In the present invention, among these curable organopolysiloxanes, curable organopolysiloxanes having T units as the main silicon-containing bond units are preferably used. Hereinafter, unless otherwise specified, curable organopolysiloxane is simply referred to as organopolysiloxane. Here, in the present specification, an organopolysiloxane having a T unit as a main constituent unit (hereinafter referred to as “organopolysiloxane (T)” as necessary) refers to an M unit, a D unit, a T unit, and The ratio of the number of T units to the total number of Q units refers to an organopolysiloxane having 50 to 100%. In the present invention, the ratio of the number of T units is more preferably 70 to 100%, particularly preferably an organopolysiloxane. Uses an organopolysiloxane having a T-unit ratio of 90 to 100%. Moreover, as other units contained in a small amount other than T units, D units and Q units are preferable, and Q units are particularly preferable.
That is, in the present invention, among these curable organopolysiloxanes, organopolysiloxanes composed only of T units and Q units, and the ratio of the number thereof is T: Q = 90 to 100: 10 to 0. Particularly preferably used.
In addition, the ratio of the number of M units, D units, T units, and Q units in the organopolysiloxane can be calculated from the value of the peak area ratio by ²⁹ Si-NMR.

The organopolysiloxane (T) preferably used in the present invention is an organopolysiloxane having T units represented by the following T1 to T3.

T1: R—Si (—OX) ₂ (—O ^* −)
T2: R—Si (—OX) (— O ^* −) ₂
T3: R—Si (—O ^* −) ₃
(In the formula, R represents a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms, X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and O ^* represents two (Represents an oxygen atom connecting silicon atoms)

  R in the chemical formula is not limited to one type, and T1, T2, and T3 may each include a plurality of types of R. Moreover, -OX in the above chemical formula represents a hydroxyl group or an alkoxy group. -OX may be the same or different between T1 and T2. Two -OX in T1 may be different, for example, one may be a hydroxyl group and the other may be an alkoxy group. Moreover, when both -OX is an alkoxy group, those alkoxy groups may be different alkoxy groups. However, as described later, usually, the two alkoxy groups are the same alkoxy group.

In addition, T unit which does not have the oxygen atom (O ^* ) which couple | bonds two silicon atoms, and has three -OX only is hereafter called T0. T0 actually corresponds to an unreacted T monomer contained in the organopolysiloxane and is not a silicon-containing bond unit. This T0 is measured in the same manner as T1 to T3 in the analysis of units of T1 to T3.

T0 to T3 in the organopolysiloxane can be analyzed by measuring the bonding state of silicon atoms in the organopolysiloxane by nuclear magnetic resonance analysis ( ²⁹ Si-NMR). The ratio of the number of T0 to T3 is determined from the peak area ratio of ²⁹ Si-NMR. -OX in the organopolysiloxane molecule can be analyzed by infrared absorption analysis. The ratio of the number of hydroxyl groups and alkoxy groups bonded to silicon atoms is determined from the peak area ratio of the infrared absorption peaks of the two. The weight average molecular weight Mw, the number average molecular weight Mn, and the dispersity Mw / Mn of the organopolysiloxane are values measured by gel permeation chromatography using polystyrene as a standard substance. The characteristics of such an organopolysiloxane do not refer to the characteristics of one molecule but are determined as the average characteristics of each molecule.

  In the organopolysiloxane (T), two or more different T1, T2, and T3, each present in a molecule, may exist. For example, two or more types of T2 with different R may exist. Such organopolysiloxanes are obtained from a mixture of two or more T monomers. For example, in an organopolysiloxane obtained from a mixture of two or more T monomers having different R, it is considered that two or more T1, T2, and T3 having different R exist. The ratio of the number of different R in the organopolysiloxane obtained from a mixture of a plurality of T monomers having different R reflects the composition ratio of the T monomer mixture having different R as a whole T unit. However, the ratio of the number of units with different R in each of T1, T2, and T3 does not necessarily reflect the composition ratio of T monomer mixtures with different R. This is because the reactivity of T monomer, T1, and T2 may differ depending on the difference in R even if three -OX in T monomer are the same.

The organopolysiloxane (T) is preferably produced from at least one T monomer represented by R—Si (—OY) ₃ . In this formula, R is the same as R described above, and Y represents an alkyl group having 1 to 6 carbon atoms. Y may be a substituted alkyl group such as an alkoxy-substituted alkyl group in addition to an unsubstituted alkyl group. Three Y in one molecule may be different. However, usually three Y are the same alkyl group. Y is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms. Specific examples of Y include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a t-butyl group, and a 2-methoxyethyl group.

  R is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms. The organic group means an organic group in which the atom bonded to the silicon atom is a carbon atom as described above.

  Examples of the unsubstituted monovalent organic group include hydrocarbon groups such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and an aralkyl group. These hydrocarbon groups include alkyl groups having 1 to 10 carbon atoms, alkenyl groups and alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 7 carbon atoms. 10 to 10 aralkyl groups are preferred. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, octyl group, decyl group, vinyl group, allyl group, cyclohexyl group, phenyl Group, benzyl group, phenethyl group and the like.

  Examples of the substituted monovalent organic group include a hydrocarbon group in which a ring hydrogen atom such as a cycloalkyl group, an aryl group, and an aralkyl group is substituted with an alkyl group, and the hydrogen atom of the hydrocarbon group is a halogen atom or a functional group And a substituted organic group substituted with a functional group-containing organic group. The functional group is preferably a hydroxyl group, mercapto group, carboxyl group, epoxy group, amino group, cyano group or the like. As the halogen atom-substituted organic group, an alkyl group having a chlorine atom or a fluorine atom such as a chloroalkyl group or a polyfluoroalkyl group is preferable. Examples of the functional group-containing organic group include an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a glycidyl group, an epoxycyclohexyl group, an alkylamino group, a dialkylamino group, an arylamino group, and an N-aminoalkyl-substituted aminoalkyl group. preferable. In particular, chlorine atom, mercapto group, epoxy group, amino group, acryloyloxy group, methacryloyloxy group, glycidyl group, alkylamino group, N-aminoalkyl-substituted aminoalkyl group and the like are preferable. The T monomer having a substituted organic group substituted with a functional group, a functional group-containing organic group or the like includes a category of compounds called silane coupling agents.

  Specific examples of the substituted organic group include the following organic groups. 3-chloropropyl group, 3,3,3-trifluoropropyl group, 3-mercaptopropyl group, p-mercaptomethylphenylethyl group, 3-acryloyloxypropyl group, 3-methacryloyloxypropyl group, 3-glycidoxy Propyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, N-phenyl-3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, 2-cyanoethyl Group.

  A particularly preferred monovalent organic group as R is an alkyl group having 1 to 4 carbon atoms. The organopolysiloxane (T) is preferably an organopolysiloxane obtained by using a T monomer having an alkyl group having 1 to 4 carbon atoms alone or two or more thereof. Moreover, the organopolysiloxane obtained by using 1 or more types of T monomer which has a C1-C4 alkyl group as organopolysiloxane (T), and a small amount of other T monomers is also preferable. The proportion of other T monomers is preferably 30 mol% or less, particularly preferably 15 mol% or less, based on the total amount of T monomers. As the other T monomer, a T monomer having a substituted organic group substituted with a functional group, a functional group-containing organic group, or the like in a category called a silane coupling agent is preferable.

Specific examples of the T monomer having an alkyl group having 1 to 4 carbon atoms include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. In particular, methyltrimethoxysilane and ethyltrimethoxysilane are preferable. Specific examples of the T monomer having a substituted organic group and the like include the following compounds.

  Vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3 -Acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-a Roh propyltrimethoxysilane, 3-cyano-ethyl trimethoxysilane.

Examples of T monomer (a = 1) represented by (R′-) _a Si (—Z) _4-a other than T monomer represented by R—Si (—OY) ₃ include methyltrichlorosilane, Examples include ethyltrichlorosilane, phenyltrichlorosilane, 3-glycidoxypropyltrichlorosilane, methyltriacetoxysilane, and ethyltriacetoxysilane.

In the D monomer (a = 2) represented by (R'-) _a Si (-Z) _4-a , two R's may be the same or different. In the case of being the same, an alkyl group having 1 to 4 carbon atoms is preferable. When they are different, it is preferable that one R ′ is an alkyl group having 1 to 4 carbon atoms and the other R ′ is a substituted organic group substituted with the functional group or the functional group-containing organic group. Moreover, as a Z group, a C1-C4 alkoxy group, an acetoxy group, etc. are preferable. Examples of the D monomer include the following compounds.

  Dimethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiacetoxysilane, 3-chloropropylmethyldimethoxysilane, 3,3,3-trifluoropropylmethyldimethoxy Silane, 3-mercaptopropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-cyanoethylmethyldimethoxysilane.

In _{(R'-) a Si (-Z)} Q monomer represented by _{4-a (a = 0)} , it may be different from four Z groups, but usually the same. The Z group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group. Examples of the Q monomer include the following compounds.

  Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane.

  The organopolysiloxane (T) used in the present invention is obtained by subjecting the above T monomer or the like to partial hydrolysis condensation. Usually, this reaction is performed by heating T monomer or the like and water in a solvent. A catalyst is preferably present in the reaction system. The desired organopolysiloxane can be produced by adjusting the reaction conditions such as the type of monomer, the amount of water, the heating temperature, the type and amount of catalyst, and the reaction time. In some cases, a commercially available organopolysiloxane can be used as it is as a target organopolysiloxane, or a target organopolysiloxane can be produced using a commercially available organopolysiloxane.

  As the catalyst, an acid catalyst is preferable. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p- An organic acid such as toluenesulfonic acid may be mentioned. In particular, acetic acid is preferred. The solvent is preferably a hydrophilic organic solvent, and particularly preferably an alcohol solvent. Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, 4-methyl-2-pentanol, 2- Examples include butoxyethanol. The reaction temperature can be reacted at room temperature when a catalyst is present. Usually, an appropriate temperature is employed from the reaction temperature of 20 to 80 ° C. according to the purpose.

  The hydrolysis-condensation reaction is a reaction in which T1 is generated from T0 (T monomer), T2 is generated from T1, and T3 is generated from T2. Condensation reaction in which at least one hydrolyzable group is converted to a hydroxyl group from T0 to T1, a condensation reaction in which at least one of two —OX is a hydroxyl group, T1 to T2 is generated, or T2 in which —OX is a hydroxyl group It is considered that the reaction rate of the condensation reaction in which T3 is generated from the reaction becomes slower in this order. Even considering the hydrolysis reaction of the hydrolyzable group, it is considered that the peak of the abundance of each unit moves from T0 to T3 as the reaction proceeds. When the reaction conditions are relatively mild, the movement of the abundance peak is considered to proceed relatively orderly. On the other hand, when the reaction conditions are relatively severe, the reaction proceeds at random, and the distribution of the abundance of each unit becomes flat, and the abundance of T0 and T1 tends to increase with respect to the abundance of T2 and T3. As will be described later, among the organopolysiloxanes (T) used in the present invention, the organopolysiloxane (a) has a small amount of T0 and T1, and the ratio of the amounts of T2 and T3 is in a specific range. It is a relatively high molecular weight organopolysiloxane, and such an organopolysiloxane can be produced by selecting relatively mild reaction conditions.

  The reactivity of the condensation reaction varies depending on R, and when R is different, the reactivity of the hydroxyl group also varies. Usually, the smaller R is (for example, when R is an alkyl group, the smaller the number of carbon atoms in the alkyl group), the higher the reactivity of the hydroxyl group. Accordingly, it is preferable to select the T monomer in consideration of the relationship between the reactivity of the hydrolyzable group and the reactivity of the hydroxyl group.

  Furthermore, the rate of hydrolysis reaction of a hydrolyzable group to a hydroxyl group varies depending on the type of hydrolyzable group, and it is preferable to consider the relationship with the rate of condensation reaction. For example, when the OX group of T2 is an alkoxy group, if the rate of the hydrolysis reaction is too slow, T2 in which the OX group is a hydroxyl group decreases. Similarly, when the rate of the hydrolysis reaction is too slow, T1 in which the OX group is a hydroxyl group decreases. For this reason, it becomes difficult to obtain a high ratio of the amount of hydroxyl groups to alkoxy groups in the organopolysiloxane. For this reason, the alkoxy group which is an OX group is preferably a highly reactive alkoxy group, that is, an alkoxy group having a low carbon number, and most preferably a methoxy group. When the reactivity of the hydrolyzable group is sufficiently high, an organopolysiloxane having a high proportion of hydroxyl groups can be obtained from an organopolysiloxane having a high proportion of hydrolyzable groups without much progress of the condensation reaction.

  In the hard coat agent composition used in the present invention, one kind of curable organopolysiloxane (T) thus obtained can be blended alone, or two or more kinds can be blended together. It is. The combination of organopolysiloxane (a) and organopolysiloxane (b) will be described below as a particularly preferred combination of organopolysiloxane (T) from the viewpoint of scratch resistance. The curable organopolysiloxane used in the present invention is described below. It is not limited to these. Further, the organopolysiloxane (a) and the organopolysiloxane (b) are not precluded from being used in the present invention alone as the organopolysiloxane (T).

(Organopolysiloxane (a))
The organopolysiloxane (a) contains each unit of T1 to T3 at a ratio of T1: T2: T3 = 0 to 5:15 to 40:55 to 85 and T3 / T2 = 1.5 to 4.0. . Further, regarding the OX group in the organopolysiloxane (a), the ratio of the number (A) that is an alkoxy group to the number (B) that is a hydroxyl group, and (B) / (A) is 12 in terms of molecular average. 0.0 or more. And the mass average molecular weight of organopolysiloxane (a) is 800-8000. The organopolysiloxane (a) does not substantially contain T0 which is a T monomer.

  The ratio of T1, T2 and T3 constituting the organopolysiloxane (a) is preferably (T2 + T3) / (T1 + T2 + T3) in the range of 0.85 to 1.00, 0.90 or more and less than 1.00 It is more preferable that Moreover, about T3 / T2, a preferable range is 2.0-4.0.

  By making the ratio of T1, T2 and T3 constituting the organopolysiloxane (a) in such a range with the average composition of each molecule, the organopolysiloxane (a) and the organopolysiloxane (b) described later can be obtained. When used in combination in the hard coat composition according to the present invention, the scratch resistance of the finally obtained hard coat layer can be improved.

  (B) / (A) in the organopolysiloxane (a) is a parameter indicating condensation reactivity. The larger this value, that is, the greater the proportion of hydroxyl groups compared to the alkoxy groups, the greater the organopolysiloxane (a). When a hard coat agent composition is formed by combining the organopolysiloxane (b) with a curing reaction during curing film formation is promoted. In addition, alkoxy groups left unreacted during the formation of the cured film may cause a decrease in scratch resistance of the finally obtained hard coat layer, and if post-curing progresses, it may cause micro cracks. The higher the proportion of hydroxyl groups compared to the groups, the better. (B) / (A) in the organopolysiloxane (a) is 12.0 or more, preferably 16.0 or more. Note that (A) may be zero.

  When the value of (B) / (A) is less than 12.0, the proportion of hydroxyl groups is too small compared to the alkoxy groups, and the effect of promoting the curing reaction cannot be obtained, and scratch resistance is caused by the influence of the alkoxy groups. This may lead to a decrease in the thickness and cause post-curing to cause microcracks. That is, when the value of (B) / (A) is less than 12.0, a three-dimensional cross-linked structure formed by a curing reaction of organopolysiloxane (a) and organopolysiloxane (b) during the formation of a cured film ( In the network), a part of the organopolysiloxane (a) is not incorporated and it is easy to bleed out, etc., so that the crosslinking density is lowered, the wear resistance is not obtained, and the curing is not sufficiently progressed. Problems occur.

  The mass average molecular weight of the organopolysiloxane (a) is 800 to 8000, preferably 1000 to 6000. When the weight average molecular weight of the organopolysiloxane (a) is in this range, when the organopolysiloxane (a) and the organopolysiloxane (b) are used in combination in the hard coat agent composition of the present invention, the final In particular, the scratch resistance of the hard coat layer obtained can be sufficiently improved.

  In the present invention, in order to obtain the organopolysiloxane (a) used in the hard coat agent composition for forming a hard coat layer particularly excellent in scratch resistance, as a raw material hydrolyzable silane compound, 70% by mass or more is methyltrialkoxysilane, preferably 1 to 4 carbon atoms in the alkoxy group. However, a small amount of T monomer other than methyltrialkoxysilane can be used in combination for the purpose of improving the adhesion, hydrophilicity, water repellency and the like.

  As a method for producing the organopolysiloxane (a), as described above, hydrolysis condensation reaction of T monomer or the like is performed in a solvent in the presence of an acid catalyst. Here, the water required for hydrolysis is usually 1 to 10 equivalents, preferably 1.5 to 7 equivalents, and more preferably 3 to 5 equivalents with respect to 1 equivalent of the monomer. When the monomer is hydrolyzed and condensed, it can also be carried out in a reaction system in which colloidal silica (described later) is present. When water-dispersed colloidal silica is used as the colloidal silica, water is supplied from this dispersion. Is done. 0.1-50 mass parts is preferable with respect to 100 mass parts of monomers, and, as for the usage-amount of an acid catalyst, 1-20 mass parts is especially preferable. As the solvent, the alcohol solvent is preferable, and from the viewpoint of good solubility of the resulting organopolysiloxane (a), specifically, methanol, ethanol, 2-propanol, 1-butanol, and 2-butanol are particularly preferable. preferable.

  Usually, the reaction temperature is 20 to 40 ° C., and the reaction time is 1 hour to several days. Although the hydrolysis and condensation reaction of the monomer is an exothermic reaction, it is preferable that the temperature of the system does not exceed 60 ° C. It is also preferable to allow the hydrolysis reaction to proceed sufficiently under such conditions, and then to proceed the condensation reaction at 40 to 80 ° C. for 1 hour to several days in order to stabilize the resulting organopolysiloxane.

  Organopolysiloxane (a) can also be produced from commercially available organopolysiloxanes. Since the commercially available organopolysiloxane is usually an organopolysiloxane having a higher proportion of alkoxy groups than the hydroxyl group, in particular, except for the above (B) / (A), commercially available similar to the desired organopolysiloxane (a). It is preferable to produce the organopolysiloxane (a) by increasing the proportion of hydroxyl groups by hydrolysis reaction using the above organopolysiloxane.

Examples of commercially available organopolysiloxane that can be used as a raw material for the organopolysiloxane (a) include the following organopolysiloxanes, which are partially hydrolyzed condensates of methyltrimethoxysilane. In addition, the notation of “ND” means that it is below the detected amount when the ²⁹ Si-NMR peak area ratio is measured using a nuclear magnetic resonance analyzer, manufactured by JEOL Ltd., ECP400 (trade name). Shown (the same applies below).

Methyl type silicone resin KR-220L (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); T0: T1: T2: T3 = ND: ND: 28:72, Si—OH / SiO—CH ₃ = 11.7, mass average molecular weight Mw = 4720, number average molecular weight Mn = 1200, Mw / Mn = 3.93.

Methyl silicone resin KR-500 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); T0: T1: T2: T3 = ND: 15: 58: 27, the peak derived from the Si—OH group was not confirmed by FT-IR, Only substantially SiO—CH ₃ exists. Mw = 1240, Mn = 700, Mw / Mn = 1.77.

  When the organopolysiloxane (a) is produced from the commercially available organopolysiloxane as described above, it is preferable to mainly hydrolyze the alkoxy group of the commercially available organopolysiloxane in the presence of an acid catalyst. For example, 0 to 10 times the amount (mass) of solvent is added to commercially available organopolysiloxane, stirred well, and then an acid aqueous solution having a concentration of about 0.1 to 70% by mass is added, and 15 to 80 ° C., preferably Is a method of stirring at a temperature of 20 to 70 ° C. for 1 to 24 hours. As the solvent to be used, an aqueous solvent can be used, and in addition, the above alcohol solvent to which water is added can also be used.

(Organopolysiloxane (b))
The organopolysiloxane (b) used in combination with the organopolysiloxane (a) in the hard coat agent composition used in the present invention is 1/10 to 1 / 1.5 times the mass average molecular weight of the organopolysiloxane (a). It is an organopolysiloxane having a mass average molecular weight of (ie, (0.1 to 0.67) times). The organopolysiloxane (b) is an organopolysiloxane having a smaller mass average molecular weight than the organopolysiloxane (a) to be combined, and has the T1 to T3 units. The ratio of the numbers of T1, T2, and T3, the ratio of T3 / T2, and the ratio of (B) / (A) described above are not particularly limited.

  The mass average molecular weight of the organopolysiloxane (b) is preferably 1/8 to 1 / 1.5 times (that is, (0.125 to 0.67) times) of the organopolysiloxane (a) to be combined. When the weight average molecular weight of the organopolysiloxane (b) exceeds 1 / 1.5 times the weight average molecular weight of the organopolysiloxane (a), in other words, the weight average molecular weight of the organopolysiloxane (a) When the mass average molecular weight of b) is less than 1.5 times, the toughness of the finally obtained hard coat layer is lowered, which causes cracks. Further, when the mass average molecular weight of the organopolysiloxane (b) is less than 1/10 times the mass average molecular weight of the organopolysiloxane (a), in other words, the mass average molecular weight of the organopolysiloxane (a) is the organopolysiloxane (b). When the weight average molecular weight of 10) exceeds 10 times, the scratch resistance of the finally obtained hard coat layer is lowered, and there is a possibility that a hard coat layer having sufficient scratch resistance cannot be obtained.

  More preferable organopolysiloxane (b) is that each silicon-containing bond unit represented by T0, T1, T2 and T3 is in the ratio of the number of these units, T0: T1: T2: T3 = 0 to 5: 0. It is an organopolysiloxane in the range of 50: 5-70: 10-90. A large ratio of T0 and T1 in the organopolysiloxane (b) generally indicates that the hydrolysis reaction or condensation reaction of the raw material monomer was insufficient when the organopolysiloxane was produced. In the organopolysiloxane (b), if the ratios of T0 and T1 are large, a hard coat agent composition containing this and the organopolysiloxane (a) is used to form cracks during thermosetting when forming a cured film. Will tend to occur more frequently. In general, when the organopolysiloxane is produced, if the condensation reaction of the raw material monomer is advanced too much, the ratio of T3 of the obtained organopolysiloxane increases. In the organopolysiloxane (b), when the ratio of T3 becomes higher than necessary, a hard coat agent composition containing this and the organopolysiloxane (a) is used, and at the time of thermal curing when a cured film is formed, Since the cross-linking reaction becomes difficult, there is a possibility that a cured film cannot be formed, and it may be impossible to finally obtain a hard coat layer having sufficient scratch resistance.

The organopolysiloxane (b) can be produced from a T monomer or the like in the same manner as the organopolysiloxane (a). Commercially available organopolysiloxane can be used as organopolysiloxane (b) as it is. Examples of commercially available organopolysiloxanes that can be used as the organopolysiloxane (b) include the following organopolysiloxanes. In addition, the notation of “trace” is 0.01 or more and 0.25 when the peak area ratio of ²⁹ Si-NMR is measured using a nuclear magnetic resonance analyzer, manufactured by JEOL Ltd., ECP400 (trade name). Indicates the following (the same applies hereinafter).

  Tosgard 510 (trade name, manufactured by Momentive Performance Materials); molecular weight: Mn = 1370, Mw = 1380, Mw / Mn = 1.01. Number of T units: (total amount of M units, D units, and Q units) = 99.9 or more: ND. T0: T1: T2: T3 = ND: 2: 36: 62.

  KP851 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); molecular weight: Mn = 1390, Mw = 1400, Mw / Mn = 1.01, number of T units: (total amount of each of M units, D units and Q units) ) = 99.9 or more: ND. T0: T1: T2: T3 = trace: 21: 58: 21.

  Here, in the hard coat agent composition used in the present invention described below, the ratio of the content of the organopolysiloxane (b) to the organopolysiloxane (a) is 1.5 to 30 times in terms of mass ratio. It is preferable that it is 2-15 times. In the hard coat agent composition used in the present invention, if both are contained in such a ratio, the organopolysiloxane three-dimensional crosslinked structure formed by the curing reaction is in the three-dimensional crosslinked structure mainly composed of the organopolysiloxane (b). The component (a), organopolysiloxane, is partially incorporated, and the hard coat layer finally obtained can have good scratch resistance.

  The hard coat agent composition used in the present invention contains the above curable organopolysiloxane, preferably organopolysiloxane (T). The content of the organopolysiloxane in the hard coat agent composition is preferably 50 to 100% by mass with respect to the total amount of the composition excluding the solvent (hereinafter referred to as “nonvolatile component” as necessary), 60 to More preferably, it is 95 mass%. In the present invention, the amount of the non-volatile component is measured based on a mass change after being held at 150 ° C. for 45 minutes.

(UV absorber)
As an ultraviolet absorber contained in the hard coat agent composition used in the production method of the present invention, an absorbance at a wavelength of 220 nm measured for an acetonitrile solution having an ultraviolet absorber concentration of 0.001% by mass under a condition of an optical path length of 1 cm is 0.2 or more. If it has the light absorption characteristic, it can use without a restriction | limiting in particular. In order to suppress yellowing of the resin substrate, the ultraviolet absorber may have an absorption characteristic that the absorbance at a wavelength of 350 nm measured by the same method as described above is 0.1 or more. The ultraviolet absorber may be a single compound or a combination of a plurality of compounds. In the case of a combination of a plurality of compounds, it is sufficient that the ultraviolet absorber mixture has the above light absorption characteristics.
In the present specification, when the absorbance of the ultraviolet absorber is simply referred to as “absorbance at wavelength λ nm”, the absorbance at wavelength λ nm measured by the same method as described above, that is, the concentration of ultraviolet absorber is 0 unless otherwise specified. The absorbance at a wavelength of λ nm measured under the condition of an optical path length of 1 cm for a 0.001 mass% acetonitrile solution.

  In order to make the light absorption characteristics within the above range, the ultraviolet absorbers are triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, hydroxybenzoate ultraviolet absorbers, benzimidazoles. 1 type (s) or 2 or more types, such as a type | system | group ultraviolet absorber, a salicylate type ultraviolet absorber, a benzylidene malonate type ultraviolet absorber, can be used.

  Examples of the triazine-based ultraviolet absorber include 2,4-bis [hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (2-hydroxy -4-hydroxymethylphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethyl) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- ( 2-hydroxyethyl) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl ] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (3-hydroxypropyl) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (3- Hydroxypropyl) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6- Diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- 2-hydroxy-4- (4-hydroxybutyl) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (4-hydroxybutyl) phenyl] -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (4-hydroxybutoxy) phenyl] -4,6-diphenyl-1,3,5-triazine 2- [2-hydroxy-4- (4-hydroxybutoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- Hydroxymethylphenyl) -4,6-bis (2-hydroxy-4-methylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethyl) phenyl] -4, 6-bis (2-hydroxy-4-methylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-bis (2-hydroxy- 4-methylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-hydroxypropyl) phenyl] -4,6-bis (2-hydroxy-4-methylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6-bis (2-hydroxy-4-methylphenyl) -1,3,5-triazine, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- (4,6-diphenyl-1,3,5- Triazine-2 Yl) -5-[(hexyl) oxy] -phenol, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3 5-triazine, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and [(C10-C16, mainly C12-C13 Alkyloxy) methyl] oxirane reaction product, 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) ) -Glycidic acid ester and the like.

  Examples of the benzophenone ultraviolet absorber include 2,2′-dihydroxy-4,4′-di (hydroxymethyl) benzophenone, 2,2′-dihydroxy-4,4′-di (2-hydroxyethyl) benzophenone, 2,2′-dihydroxy-3,3′-dimethoxy-5,5′-di (hydroxymethyl) benzophenone, 2,2′-dihydroxy-3,3′-dimethoxy-5,5′-di (2-hydroxy) Ethyl) benzophenone, 2,2′-dihydroxy-3,3′-di (hydroxymethyl) -5,5′-dimethoxybenzophenone, 2,2′-dihydroxy-3,3′-di (2-hydroxyethyl)- 5,5′-dimethoxybenzophenone, 2,2-dihydroxy-4,4-dimethoxybenzophenone and the like can be mentioned.

  Examples of the benzotriazole ultraviolet absorber include 2- [2′-hydroxy-5 ′-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(2-hydroxyethyl). ) Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-methyl-5'- (Hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-methyl-5 ′-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy- 3′-methyl-5 ′-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-( Hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-t-butyl-5 ′-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy -3′-t-butyl-5 ′-(2-hydroxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-3′-t-butyl-5 ′-(3- Hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-t-octyl-5 ′-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 '-T-octyl-5'-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-octyl-5 '-(3-hydroxypro ) Phenyl] -2H-benzotriazole or the like, or 2,2′-methylenebis [6- (2H-benzotriazoly-2-yl) -4- (hydroxymethyl) phenol], 2,2 ′;-methylenebis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2'-methylenebis [6- (5-chloro-2H-benzotriazoly-2-yl) -4- (2-hydroxy Ethyl) phenol], 2,2'-methylenebis [6- (5-bromo-2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2'-methylenebis [6- (2H -Benzotriazoly-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylenebis [6- (5-chloro-2H-benzoto) Reazoly-2-yl) -4- (3-hydroxypropyl) phenol], 2,2′-methylenebis [6- (5-bromo-2H-benzotriazoly-2-yl) -4- (3-hydroxypropyl) phenol ], 2,2'-methylenebis [6- (2H-benzotriazoly-2-yl) -4- (4-hydroxybutyl) phenol], 2,2'-methylenebis [6- (5-chloro-2H-benzotriazoly- 2-yl) -4- (4-hydroxybutyl) phenol], 2,2′-methylenebis [6- (5-bromo-2H-benzotriazoly-2-yl) -4- (4-hydroxybutyl) phenol], 3,3- {2,2′-bis [6- (2H-benzotriazoly-2-yl) -1-hydroxy-4- (2-hydroxyethyl) phenyl]} propane, 2- {2,2′-bis [6- (2H-benzotriazoly-2-yl) -1-hydroxy-4- (2-hydroxyethyl) phenyl]} butane, 2,2′-oxybis [6- (2H -Benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2′-bis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol] sulfide, 2,2′-bis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol] sulfoxide, 2,2′-bis [6- (2H-benzotriazoly-2-yl)- 4- (2-hydroxyethyl) phenol] sulfone, 2,2′-bis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol] amine, and the like. I can get lost.

  Examples of the cyanoacrylate ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and the like.

  Hydroxybenzoate UV absorbers include phenyl salicylate, 4-t-butylphenyl salicylate, 2,5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t -Butylphenyl-3 ', 5-di-t-butyl-4'-hydroxybenzoate and the like.

  Examples of the benzimidazole ultraviolet absorber include phenylbenzimidazole-5-sulfonic acid and its salt, phenylene-bis-benzimidazole-tetrasulfonic acid and its salt, and the like.

  Examples of salicylate ultraviolet absorbers include p-tert-butylphenyl salicylate, phenyl salicylate, p-octylphenyl salicylate, and the like.

  Examples of the benzylidene malonate ultraviolet absorber include dimethyl-4-methoxybenzylidene malonate, tetraethyl-2,2 '-(1,4-phenylene-dimethylidene) -bismalonate, and the like.

Specific examples of UV absorbers suitable for the production method of the present invention are structural formulas, absorbance A ₂₂₀ (Spectraphotometer SolidSpec-3700DUV manufactured by Shimadzu Corporation, optical path length for acetonitrile solution having a concentration of 0.001% by mass. The absorbance at a wavelength of 220 nm measured at 1 cm) is shown below together with examples of commercially available products.

First, as a triazine UV absorber, 2- [4- (4,6-bis-biphenyl-4-yl- [1,3,5] triazin-2-yl)-represented by the following structural formula (1): 3-Hydroxy-phenoxy] -propionic acid 6-methyl-heptyl ester (absorbance A ₂₂₀ : 0.41, commercially available product: TINUVIN 479 (trade name, manufactured by Ciba Japan), etc.), represented by the following structural formula (2) 2- [4- (4,6-bis- {2-hydroxy-4- [1- (6-methyl-heptyloxycarbonyl) -ethoxy] -phenyl}-[1,3,5] triazine-2- yl) -3-hydroxy - phenoxy] - propionic acid 6-methyl - heptyl ester (absorbance _A 220: 0.27, commercially available: CGL777 (trade name, manufactured by Ciba Japan K.K.), etc.), the following structural formula Represented by 3) 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and the reaction product of oxirane (absorbance _{A 220} : 0.25, commercially available product: TINUVIN 400 (trade name, manufactured by Ciba Japan Co., Ltd.), etc., 2,4-bis [2-hydroxy-4-butoxyphenyl] -6 represented by the following structural formula (4) (2,4-dibutoxyphenyl) -1,3,5-triazine (absorbance A ₂₂₀ : 0.46, commercially available product: TINUVIN 460 (trade name, manufactured by Ciba Japan Co., Ltd.)), the following structural formula (5) Reaction of 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester represented by Product (absorbance _220: 0.40, commercially available products: TINUVIN 405 (trade name, manufactured by Ciba Japan Co., Ltd.) and the like).

Further, as a benzophenone-based ultraviolet absorber, 4,6-dibenzoylresorcinol (DBR) (absorbance A ₂₂₀ : 0.36) represented by the following structural formula (6), 2,4 represented by the following structural formula (7) - dihydroxybenzophenone (DHBP) (absorbance _A 220: 0.62) and the like.

Furthermore, as a benzotriazole ultraviolet absorber, octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) represented by the following structural formula (8) Propyl] propionate (absorbance A ₂₂₀ : 0.44, commercially available product: TINUVIN 109 (trade name, manufactured by Ciba Japan), etc.), 2- (2H-benzotriazol-2-yl represented by the following structural formula (9) ) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (absorbance A ₂₂₀ : 0.58, commercial product: TINUVIN 928 (trade name, Ciba)・ Made in Japan))) and the like.

Among these UV absorbers, 2- [4- (4,6-bis-biphenyl-4-yl- [1,3,5] triazin-2-yl) -3-hydroxy-phenoxy] -propionic acid 6-methyl-heptyl ester, 2- [4- (4,6-bis- {2-hydroxy-4- [1- (6-methyl-heptyloxycarbonyl) -ethoxy] -phenyl}-[1,3 5] Triazin-2-yl) -3-hydroxy-phenoxy] -propionic acid 6-methyl-heptyl ester, 4,6-dibenzoylresorcinol, octyl-3- [3-tert-butyl-4-hydroxy-5 (5-Chloro-2H-benzotriazol-2-yl) propyl] propionate, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenyl) Chill) -4- (1,1,3,3-tetramethylbutyl) phenol, on the absorbance _{A 220} is high, since high 350nm absorbance is more preferably used.

Although content in particular of the ultraviolet absorber in a hard-coat agent composition is not restrict | limited, Usually, it is 1-15 mass parts with respect to 100 mass parts of organopolysiloxane. The ultraviolet absorber is preferably 2 to 5 parts by mass, more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the organopolysiloxane so that the curing reaction by Xe ₂ excimer light irradiation proceeds promptly and sufficiently. preferable.

(Optional component)
The hard coat agent composition used in the present invention may contain various additives in addition to the organopolysiloxane and the ultraviolet absorber. For example, in order to further improve the scratch resistance of the hard coat layer of the resin substrate with a hard coat layer of the present invention, a hard coat agent composition containing silica fine particles is preferable. For this reason, it is preferable to add colloidal silica to the hard coat agent composition. Colloidal silica refers to silica fine particles dispersed in water or an organic solvent such as methanol, ethanol, isobutanol, or propylene glycol monomethyl ether.

  The silica fine particles can also be blended with the raw material monomer in the production process of the organopolysiloxane. By producing organopolysiloxane in a reaction system containing colloidal silica, an organopolysiloxane containing silica fine particles can be obtained. For example, a T monomer and, if necessary, water or an acid catalyst are added to colloidal silica, and the organopolysiloxane can be produced in the colloidal silica dispersion medium as described above. By using the organopolysiloxane thus obtained, a hard coat agent composition used in the present invention containing silica fine particles can be produced.

  The silica fine particles used in the hard coat agent composition according to the present invention preferably have an average particle size (BET method) of 1 to 100 nm. If the average particle diameter exceeds 100 nm, the particles diffusely reflect light, and thus the value of the haze value of the obtained hard coat layer becomes large, which may be undesirable in terms of optical quality. The average particle size is more preferably 5 to 40 nm. This is to maintain the transparency of the hard coat layer while imparting scratch resistance to the hard coat layer. Although colloidal silica can use both a water dispersion type and an organic solvent dispersion type, it is preferable to use a water dispersion type. It is more preferable to use colloidal silica dispersed in an acidic aqueous solution. Colloidal silica may contain inorganic fine particles other than silica fine particles such as alumina sol, titanium sol, and ceria sol.

  As content of the silica fine particle in the hard-coat agent composition used for this invention, the quantity used as 1-50 mass% is preferable with respect to the composition (nonvolatile component) whole quantity except a solvent, and it becomes 5-40 mass%. The amount is more preferred. If the content of the silica fine particles in the non-volatile component in the hard coat agent composition used in the present invention is less than 1% by mass, sufficient scratch resistance may not be ensured in the resulting hard coat layer, and the content is 50% by mass. If it exceeds 50%, the proportion of the organopolysiloxane in the non-volatile component becomes too low, and it becomes difficult to form a cured film by curing the organopolysiloxane, and cracks occur in the finally obtained hard coat layer, silica. There is a risk that the transparency of the hard coat layer is reduced due to aggregation of the fine particles.

  In addition, the hard coat agent composition used in the present invention may contain additives such as an antifoaming agent and a viscosity modifier for the purpose of improving the coatability, and for the purpose of improving the adhesion to the primer layer and the like. Additives such as an adhesion-imparting agent may be included, and a leveling agent may be included as an additive for the purpose of improving the coatability and smoothness of the resulting coating film. The amount of these additives is preferably 0.01 to 2 parts by mass for each additive component with respect to 100 parts by mass of the organopolysiloxane. Moreover, the hard-coat agent composition used for this invention may contain dye, a pigment, a filler, etc. in the range which does not impair the objective of this invention.

  In the present invention, in order to prevent gelation of the hard coat agent composition at room temperature and increase the storage stability, it is preferable to adjust the pH of the hard coat agent composition to 3.0 to 6.0, It is more preferable to adjust to 4.0 to 5.5. Under conditions where the pH is 2.0 or lower or 7.0 or higher, the hydroxyl group bonded to the silicon atom is extremely unstable, and thus is not suitable for storage. Examples of the pH adjustment method include addition of an acid and adjustment of the content of the curing catalyst. Examples of acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p-toluene Examples include organic acids such as sulfonic acid.

  The hard coat agent composition used in the present invention is usually prepared in a form in which an organopolysiloxane and an ultraviolet curing agent, which are essential components, and various additives, which are optional components, are dissolved and dispersed in a solvent. It is necessary for all the non-volatile components in the hard coat agent composition to be stably dissolved and dispersed in a solvent. For this reason, the solvent preferably contains 20% by mass or more, more preferably 50% by mass or more of alcohol. .

  Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 4-methyl- 2-Pentanol, 2-butoxyethanol, and the like are preferable. Among these, alcohol having a boiling point of 80 to 160 ° C. is preferable from the viewpoint of good solubility of the organopolysiloxane and good coating property. Specifically, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 4-methyl-2- Pentanol and 2-butoxyethanol are preferred.

  The solvent used in the hard coat agent composition according to the present invention includes a lower alcohol generated by hydrolyzing a raw material monomer, for example, an alkyltrialkoxysilane, and water when producing an organopolysiloxane, In the case of using water in the dispersed colloidal silica that does not participate in the hydrolysis reaction and colloidal silica in an organic solvent dispersion system, the dispersed organic solvent is also included.

  Furthermore, in the hard-coat agent composition used for this invention, you may use together other solvents other than the alcohol which can be mixed with water / alcohol as a solvent other than the above. Examples of such solvents include ketones such as acetone and acetylacetone; esters such as ethyl acetate and isobutyl acetate; ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and diisopropyl ether.

  The amount of the solvent used in the hard coat agent composition according to the present invention is preferably 50 to 3000 parts by mass, and 150 to 2000 parts by mass with respect to 100 parts by mass of all nonvolatile components in the hard coat agent composition. More preferably.

  The hard coat agent composition used in the present invention can be obtained by uniformly mixing the various components described above by ordinary methods.

(1-3) Application / Curing In the (1) cured film forming step of the production method of the present invention, the hard coat agent composition prepared as described above is applied onto at least one surface of the resin substrate. Then, a coating film of the hard coating agent composition is formed, and the resulting coating film is cured. When the resin substrate with a hard coat layer has various functional layers such as a primer layer between the resin substrate and the hard coat layer, the hard coat agent composition is applied on the functional layer such as the primer layer and cured.

  Although it does not specifically limit as a method of apply | coating the said hard-coat agent composition, Normal coating methods, such as a spray coat method, a dip coat method, a flow coat method, are mentioned. It is preferable to appropriately adjust the viscosity, solid content concentration and the like of the hard coat agent composition according to the coating method to be used.

  You may perform drying operation as needed after apply | coating a hard-coat agent composition. For drying, after the hard coating agent composition is applied onto the resin substrate as described above, the coating layer is subjected to, for example, room temperature to a temperature of less than 50 ° C. for a certain time, for example, 1 minute to 0.5 hour. It is carried out by placing it to a certain extent, whereby part or all of the solvent in the coating layer is removed. As a drying condition of the solvent, from the viewpoint of application to a continuous coating process, 1 minute to 10 minutes is preferable under a temperature condition of room temperature to 40 ° C. The solvent may be removed by vacuum drying or the like while adjusting the degree of vacuum.

  The thickness (thickness before curing) of the coating film formed by applying the hard coat agent composition to the surface of a resin substrate or the like depends on the solid content concentration in the composition. It is preferable to adjust the solid content appropriately so that the film thickness after curing is within a predetermined range.

  The film thickness of the cured film applied on the resin substrate is preferably 0.1 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less in the state after curing described below, and more preferably 2 μm or more and 2 μm or more. A thickness of 10 μm or less is particularly preferable. In the production method of the present invention, the film thickness is not changed by (2) oxidation treatment / heat treatment further applied to the obtained cured film after the coating film is cured. Therefore, the film thickness after curing, that is, the film thickness of the cured film may be treated as the final film thickness of the hard coat layer finally obtained. If the thickness of the hard coat layer is too small, it may be difficult to ensure sufficient scratch resistance even by the production method of the present invention. On the other hand, if the thickness of the hard coat layer is too large, cracks and peeling may occur easily. Therefore, in order to suppress the occurrence of cracks and peeling while ensuring sufficient scratch resistance, the film thickness of the cured film (that is, the film thickness of the hard coat layer excluding the film thickness of the functional layer such as the primer layer) ) Is preferably 0.1 μm or more and 20 μm or less.

Thus, the organopolysiloxane is cured by subjecting the coating film of the hard coat agent composition formed on at least one surface of the resin substrate or the like to Xe ₂ excimer light irradiation treatment. In the present specification, there is a case where “the hard coat agent composition is cured”, which means that the organopolysiloxane contained in the hard coat agent composition is cured.

In the production method of the present invention, after the optional drying, the Xe ₂ excimer light irradiation treatment is performed without performing the heat treatment conventionally performed to cure the coating film of the hard coating agent composition, A cured film is formed only by treatment.

Xe ₂ excimer light used in this Xe ₂ excimer light irradiation treatment, an ultraviolet wavelength 172 nm. As described above, the coating film formed on the surface of a resin substrate or the like contains an ultraviolet absorber having an absorbance at a wavelength of 220 nm of 0.2 or more. Therefore, by irradiating Xe ₂ excimer light, the ultraviolet absorber At the same time, the organopolysiloxane contained in the coating film is condensed and cured to form a cured film. That is, a condensation reaction occurs between hydroxyl groups bonded to silicon atoms, and a three-dimensional structure is formed by siloxane bonds. At the same time, the bond between silicon atoms and carbon atoms present on the surface and inside of the coating film is specifically cleaved to generate radicals such as Si. That is, the coating film has a monovalent organic group derived from the raw material organopolysiloxane, such as —SiCH ₃ or —SiC ₂ H ₅ in which an alkyl group such as a methyl group or an ethyl group is bonded to a silicon atom. Present, especially on the surface of the coating. By irradiating with Xe ₂ excimer light, all or part of the bond between these silicon atoms and carbon atoms is broken. As will be described later, the Si radicals generated here are oxidized in a subsequent process to be in a state where hydroxyl groups are bonded to silicon atoms, and these hydroxyl groups are condensed to form a hardened film with higher hardness.

In this way, in the production method of the present invention, Xe ₂ excimer light irradiation is used as a means for curing the coating film. This is because Xe ₂ excimer light having a wavelength of 172 nm is irradiated with ultraviolet rays having other wavelengths. In comparison with the above, the organopolysiloxane can be condensed and cured quickly and sufficiently, and the bond between the silicon atom and the carbon atom can be effectively cut.

Here, when the surface of the coating film is irradiated with Xe ₂ excimer light, if oxygen is present in the atmosphere, oxygen selectively absorbs the Xe ₂ excimer light, so that the Xe ₂ excimer that reaches the surface of the coating film is reached. The amount of light decreases, the condensation reaction does not proceed sufficiently, and the efficiency of breaking the silicon atom-carbon atom bond also decreases. Oxygen is converted into ozone by irradiation with Xe ₂ excimer light, and the generated ozone may cause deterioration of the coating film surface, the primer layer, and further the resin substrate. Therefore, the Xe ₂ excimer light irradiation to the coating film of the hard coat agent composition formed on the resin substrate is performed under a low oxygen concentration atmosphere, preferably the oxygen concentration is 5% by volume or less, more preferably 3% by volume or less, More preferably, it is carried out in an atmosphere of 1% by volume or less. Specifically, it is preferably performed in an atmosphere that does not absorb Xe ₂ excimer light and is gas-substituted with an inert gas such as nitrogen or argon that is not affected by Xe ₂ excimer light irradiation. Here, “oxygen concentration (volume%)” represents the amount (capacity) of oxygen present per unit volume in an atmosphere in which Xe ₂ excimer light irradiation is performed, expressed as a percentage of the unit volume.

In the Xe ₂ excimer light irradiation treatment on the coating film surface of the hard coating agent composition, it is preferable that the Xe ₂ excimer light irradiation energy on the coating film surface is 600 to 18000 mJ / cm ² , preferably 1800 to 12000 mJ. / Cm ² is more preferable, and 3000 to 9000 mJ / cm ² is particularly preferable. When the Xe ₂ excimer light irradiation energy is less than 600 mJ / cm ² , the condensation reaction does not proceed sufficiently, and it may not be possible to impart sufficient scratch resistance to the finally obtained hard coat layer. On the other hand, if the Xe ₂ excimer light irradiation energy is larger than 18000 mJ / cm ² , the occurrence of cracks and the like due to contraction stress due to chemical contraction may be promoted.

In the production method of the present invention, Xe ₂ excimer light irradiation on the coating film surface of the hard coat agent composition can be performed specifically using an Xe ₂ excimer UV lamp. The Xe ₂ excimer UV lamp is not particularly limited, and the Xe ₂ excimer UV lamp used for irradiating Xe ₂ excimer light in various applications can be used in the production method of the present invention. As such a Xe ₂ excimer UV lamp, there is an excimer irradiation device as a commercial product. For example, a standard excimer light irradiation unit (irradiance: 10 mW / cm ² , manufactured by USHIO INC.), A separate excimer ultraviolet irradiation device ( Irradiance: 35 mW / cm ² , manufactured by Iwasaki Electric Co., Ltd.), lamp house type excimer UV light source (E500-172, irradiance: 10 mW / cm ² , manufactured by Excimer), etc. can be used, and the shape of the resin substrate It may be appropriately selected according to the above.

Xe ₂ excimer light irradiation is performed using such an Xe ₂ excimer UV lamp. For example, when irradiation treatment is performed using an Xe ₂ excimer UV lamp having an irradiance of 10 mW / cm ² , Xe on the cured film surface is used. _In order to make the excimer light irradiation energy within the above preferable range, the hard coat agent composition having a predetermined area at a distance of about 0.1 to 10 mm from the lamp by installing the lamp in a sealable chamber A resin substrate having a cured film of the product is disposed so that the cured film faces the lamp so that the entire surface of the cured film can be uniformly irradiated with Xe ₂ excimer light, and is placed in a nitrogen gas atmosphere for 1 to 30 minutes. For example, Xe ₂ excimer light irradiation may be performed. In order to improve the productivity by applying to a continuous coating process, which is one of the objects of the present invention, the irradiation time is preferably 1 to 15 minutes.

(2) Oxidation treatment / heat treatment step In the (2) oxidation treatment / heat treatment step of the production method of the present invention, the cured film formed in the Xe ₂ excimer light irradiation step is subjected to an oxidation treatment, followed by a heat treatment to form a hard coat layer It is a process.

The oxidation treatment is usually sufficiently performed by taking the cured film after the Xe ₂ excimer light irradiation step into the air from the low oxygen concentration atmosphere. However, if necessary, the oxidation treatment can be actively performed by a method such as exposure to dry air, oxygen atmosphere, or water vapor atmosphere immediately after the excimer light irradiation step.

By this oxidation treatment, the Si radicals on the surface of the cured film generated in the Xe ₂ excimer light irradiation step are oxidized to be in a state where a hydroxyl group is bonded to a silicon atom (—SiOH). In the production method of the present invention, a hard coat layer having sufficient scratch resistance can be obtained by subjecting the cured film in this state to a heat treatment to form a siloxane bond on the surface of the cured film to produce a high hardness surface. Is what you get.

  The temperature condition in this heat treatment is preferably not more than the heat deformation temperature of the resin substrate. However, if the temperature is too low, it takes time to cure and there is a possibility that sufficient hardness cannot be obtained. Therefore, the lower limit is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 70 ° C. or higher. On the other hand, if the temperature is too high, a siloxane bond is rapidly formed, which may lead to generation of cracks. From this viewpoint, the upper limit is preferably less than 100 ° C. Specifically, when bisphenol A-based polycarbonate resin is used for the resin substrate, a range of 50 to 140 ° C is preferable, a range of 60 to 130 ° C is more preferable, and a range of 80 to 100 ° C is even more preferable.

  As the heating means, a natural convection type thermostat, a constant temperature drier, a hot air circulation drier, a blower drier, a vacuum drier, or the like is used. An electric furnace or the like can also be used. Furthermore, a heating means using an infrared lamp can be used as appropriate. These heating means may be used alone or in combination of two or more.

  The time required for the heat treatment in the production method of the present invention is such that -SiOH on the cured film surface after the oxidation treatment sufficiently reacts to form a siloxane bond (-Si-O-Si-). Although it will not restrict | limit in particular, from a viewpoint of application to a continuous coating process, 1 to 30 minutes are preferable, 1 to 20 minutes are more preferable, and 1 to 15 minutes are still more preferable.

(Formation of primer layer)
In the resin substrate with a hard coat layer to which the production method of the present invention is applied, a primer layer may be provided between the resin substrate and the hard coat layer, which improves the adhesion between the resin substrate and the hard coat layer. Therefore, it is preferable to have a primer layer. The primer layer is not particularly limited, but in the present invention, the primer layer is preferably formed by applying a primer composition containing an acrylic polymer, an ultraviolet absorber, and a solvent on a resin substrate and drying it.

  As such an acrylic polymer, a homopolymer having at least one selected from an acrylic acid ester or a methacrylic acid ester having an alkyl group having an alkyl group having 6 or less carbon atoms as a “main monomer”, Copolymers are preferred. Here, the “main monomer” specifically refers to one having 90 to 100 mol% with respect to the whole raw material monomer, and the same shall apply hereinafter. Further, a copolymer of the above main monomer and at least one other acrylic ester or methacrylic ester is also preferable. Examples of the other monomers include acrylic acid esters and methacrylic acid esters having an alkyl group having 7 or more carbon atoms and a cycloalkyl group having 12 or less carbon atoms. In addition to these monomers, copolymers obtained by copolymerizing a small amount of an acrylic ester or methacrylic ester having a functional group-containing alkyl group (for example, a hydroxyalkyl group) can also be used. Examples of the cycloalkyl group include a cyclohexyl group, a 4-methylcyclohexyl group, a 4-t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyloxyethyl group.

  Among these, the acrylic polymer used in the present invention is preferably a polymer obtained by polymerizing one or more selected from methacrylic acid alkyl esters as main monomer units. Further, one or more of alkyl methacrylates having 6 or less carbon atoms in the alkyl group selected from methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, ethyl methacrylate, isobutyl methacrylate, etc. Homopolymers or copolymers obtained by polymerization as the main monomer are preferred. Homopolymers such as methyl methacrylate, tert-butyl methacrylate and ethyl methacrylate, methyl methacrylate and n-butyl methacrylate, ethyl methacrylate, methacryl A copolymer with one or more selected from isobutyl acid is more preferable.

  In addition, an acrylic polymer obtained by polymerizing / copolymerizing at least one selected from acrylic monomers in which a hydrolyzable silyl group and / or SiOH group is bonded via a C—Si bond can also be employed.

  Examples of the acrylic monomer include 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-methacryloyloxypropyl. Examples thereof include methyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-acryloyloxypropylmethyldimethoxysilane.

  The acrylic polymer used for forming the primer layer preferably has a mass average molecular weight of 20,000 or more, more preferably 50,000 or more, and preferably 1 million or less. Acrylic polymers having a weight average molecular weight within this range are preferable because they exhibit sufficient adhesion and strength performance as a primer layer.

  The primer layer may contain an ultraviolet absorber in order to suppress yellowing of the resin substrate. As the ultraviolet absorber, those having a light absorption property that the absorbance at a wavelength of 350 nm is 0.1 or more are preferable. The ultraviolet absorber may be a single compound or a combination of a plurality of compounds. In the case of a combination of a plurality of compounds, it is sufficient that the ultraviolet absorber mixture has the above light absorption characteristics.

  In order to make the light absorption characteristics within the above range, the ultraviolet absorber is the same as the ultraviolet absorber contained in the hard coat agent composition of the present invention, that is, a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, and a benzotriazole. Use one or more of UV-based UV absorbers, cyanoacrylate-based UV absorbers, hydroxybenzoate-based UV absorbers, benzimidazole-based UV absorbers, salicylate-based UV absorbers, benzylidene malonate-based UV absorbers, etc. Can do. The content of the ultraviolet absorber in the primer layer is preferably 1 to 50 parts by mass and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the resin component such as an acrylic polymer.

  The primer layer may further contain a light stabilizer and the like. Examples of the light stabilizer include hindered amines; nickel complexes such as nickel bis (octylphenyl) sulfide, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, and the like. . Two or more of these may be used in combination. The content of the light stabilizer in the primer layer is preferably 0.1 to 50 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of a resin component such as an acrylic polymer.

  The primer composition used for forming the primer layer usually contains a solvent. The solvent is not particularly limited as long as it can dissolve the acrylic polymer stably. Specifically, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane; esters such as ethyl acetate, butyl acetate and methoxyethyl acetate Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol, 1 Alcohols such as methoxy-2-propanol and diacetone alcohol; hydrocarbons such as n-hexane, n-heptane, isoctane, benzene, toluene, xylene, gasoline, light oil, kerosene; acetonitrile, nitromethane, water, etc. It is done. Two or more of these may be used in combination.

  The amount of the solvent is preferably 50 to 10,000 parts by mass, particularly preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of the resin component such as an acrylic polymer. In addition, it is preferable that it is 0.5-75 mass% with respect to the composition whole quantity, and, as for content of the non-volatile component (solid content) in a primer composition, it is especially preferable that it is 1-40 mass%.

  The primer composition may further contain additives such as a leveling agent, an antifoaming agent, and a viscosity modifier.

  A method for applying the primer composition onto the resin substrate is not particularly limited, and examples thereof include a spray coating method, a dip coating method, and a flow coating method. Moreover, although the heating conditions for drying are not specifically limited, It is preferable that it is 5 minutes-3 hours at 50-140 degreeC.

  The primer layer formed on the resin substrate using the primer composition may have an insufficient effect of improving the adhesion between the resin substrate and the hard coat layer if the primer layer is too thin. Therefore, the film thickness may be any film thickness that is necessary for sufficiently bonding the resin substrate and the hard coat layer and maintaining the necessary amount of the additive. The thickness of such a primer layer is preferably from 0.1 μm to 10 μm, particularly preferably from 2 μm to 8 μm.

  In addition, when the resin substrate with a hard coat layer which is the object of the production method of the present invention has the primer layer, the hard substrate is formed on the primer layer thus formed in the same manner as described above. By forming the coat layer, a resin substrate with a hard coat layer can be produced according to the present invention.

<Resin substrate with hard coat layer>
The resin substrate with a hard coat layer obtained by the production method of the present invention has a three-dimensional cross-linking structure (network) formed by a siloxane bond in the hard coat layer, and a siloxane bond on the surface side compared to the inside of the hard coat layer. Has a structure formed more firmly. The resin substrate with a hard coat layer having a hard coat layer having such a structure has a hardness gradient in the depth direction of the hard coat layer and has a high hardness surface. Has scratching properties.

Here, when obtaining the “hardness” of a thin film material such as a resin substrate with a hard coat layer of the present invention, that is, mechanical strength such as scratch resistance, evaluation is generally performed using a microhardness measurement test. It can be carried out. The microhardness measurement test is a test method that calculates the hardness from the penetration depth of the indenter under a certain load condition on the measurement surface, and thereby knows the Martens hardness corresponding to the scratch hardness. Can do.
This hardness serves as a guideline indicating the scratch resistance. However, in the resin substrate with a hard coat layer obtained by the production method of the present invention, only the Xe ₂ excimer light irradiation treatment is performed in the cured film forming step, and the heat treatment is performed. Despite not performing heat treatment, or having a Martens hardness on the surface of the hard coat layer equal to or higher than that of a conventional film formed by performing Xe ₂ excimer light irradiation treatment after heat treatment, It can be said that it has scratch resistance comparable to that of a conventional resin substrate with a hard coat layer.

In the resin substrate with a hard coat layer obtained by the production method of the present invention, the Martens hardness on the surface of the hard coat layer has a value of about 200 to 850 N / mm ² at a depth of 150 nm from the surface. It is preferable.

The resin substrate with a hard coat layer obtained by the production method of the present invention has a cured film formed only by the Xe ₂ excimer light irradiation treatment and does not require a heat treatment, and thus can be applied to a continuous process in the production. , Can increase its productivity. Further, since there is no need for heat treatment, it is not necessary to consider the thermal deformation of the resin substrate during the formation of the cured film, and therefore the degree of freedom in selecting the resin substrate to be used can be increased.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples. Examples 1 to 3 are examples, and examples 4 to 10 are comparative examples. The organopolysiloxane was analyzed by the following method.

(1) Number of silicon atom-bonded hydroxyl groups (B) / Number of silicon atom-bonded alkoxy groups (A)
Hereinafter, the organopolysiloxane used in the embodiment, as the silicon atom-bonded alkoxy groups, because it was the only one having silicon-bonded methoxy groups (SiO-CH _3), as the (B) / (A), the following The ratio of Si—OH / SiO—CH ₃ determined by the method was used. Infrared absorption spectrometer (FT-IR, Thermo Fisher Scientific Co., Model: Avatar / Nicolet FT-IR360) using, Si absorption and 900cm around ^-1 derived from SiO-CH ₃ in the vicinity of 2860Cm ^-1 The ratio of Si—OH / SiO—CH ₃ was determined from the area ratio of absorption derived from —OH.

(2) Analysis of bonding state of silicon atom in organopolysiloxane Bonding state of silicon atom in organopolysiloxane contained in hard coat agent composition, specifically, M unit, D unit, T unit, Q unit The existence ratio of T0 and the abundance ratio of T0 to T3 were determined from the peak area ratio of ²⁹ Si-NMR, respectively, using a nuclear magnetic resonance analyzer ( ²⁹ Si-NMR: manufactured by JEOL Ltd., ECP400). The measurement conditions are as follows.
・ Uses polytetrafluoroethylene (PTFE) 10mmφ sample tube,
Probe: T10
-Resonance frequency 79.42MHz,
・ Pulse width 10μsec,
・ Wait time 20sec,
・ Total number of times 1500
Relaxing reagent: containing 0.1% by mass of Cr (acac) ₃
External standard sample: tetramethylsilane.
The chemical shift of ²⁹ Si-NMR derived from each structure is as follows in the case of methyl-based organopolysiloxane.

(M unit to Q unit)
M unit: 15-5 ppm,
D unit: -15 to -25 ppm,
-T unit: -35 to -75 ppm,
-Q unit: -90 to -130 ppm.

(T0-T3)
T0: -40 to -41 ppm,
T1: -49 to -50 ppm,
T2: -57 to -59 ppm,
T3: -66 to -70 ppm.

(3) Number average molecular weight Mn, mass average molecular weight Mw, and dispersity Mw / Mn
It was determined by gel permeation chromatography (GPC, Waters 2695 manufactured by Waters, RI detection, column: Styragel guard column + HR1 + HR4 + HR5E, eluent: chloroform).

[1] Synthesis of organopolysiloxane (a) (MSi-1) In a 0.2 L flask, methyl silicone resin KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd., peak derived from Si-OH group was confirmed by FT-IR. However, it is substantially only SiO—CH _3. The abundance ratio of each T unit is T0: T1: T2: T3 = ND: 15: 58: 27, Mn = 700, Mw = 1240, Mw / Mn = 1.77. ) (10 g) and 1-butanol (10 g) were added and stirred well. Acetic acid (10 g) and ion-exchanged water (10 g) were added and further stirred. This solution was stirred at 40 ° C. for 1 hour to obtain organopolysiloxane (a) (MSi-1). This MSi-1 containing solution (MSi-1 concentration: 25% by mass) was used as it was for the preparation of [3] hard coat agent composition described later.

When the obtained MSi-1 was compared with the raw material KR-500 by FT-IR, the decrease in the peak derived from the SiO—CH ₃ group and the appearance of the peak derived from the Si—OH group were confirmed. . The ratio of Si—OH / SiO—CH ₃ of MSi-1 obtained from the peak area ratio of FT-IR was 41.0. MSi-1 consists only of T units, and the abundance ratio of each T unit determined from the chemical shift of ²⁹ Si-NMR is T0: T1: T2: T3 = ND: 1.1: 30.1: 68.8. there were. Mn of MSi-1 was 520, Mw was 1150, and Mw / Mn was 2.22.

[2] Synthesis of organopolysiloxane (b) (PSi-1) and preparation of composition solution of organopolysiloxane (b) (PSi-1) Water-dispersed colloidal silica having an average particle size of about 15 nm in a 1 L flask (PH 3.1, solid content of silica fine particles 35% by mass) 200 g and acetic acid 0.2 g were charged, and methyltrimethoxysilane 138 g was added. After stirring for 1 hour, the composition was aged at 25 ° C. for 4 days to ensure that a partially hydrolyzed condensate was formed in the silica-methanol-water dispersion.

This composition has a non-volatile component of 40% by mass, and the obtained organopolysiloxane (organopolysiloxane (b) (PSi-1)) has a bond structure mainly composed of T units (number of T units: M units and D units). The total number of each unit and Q unit = 100: 0), and the abundance ratio of each T unit determined from the chemical shift of ²⁹ Si-NMR is T0: T1: T2: T3 = ND (not detected) : 2: 54: 44. The obtained organopolysiloxane is almost free of monomeric T0 form [R-Si (OH) ₃ ] (R is a monovalent organic group), and the raw material methyltrimethoxysilane is an oligomeric organopolysiloxane. It was confirmed that it was almost completely converted. Mn of the obtained organopolysiloxane (b) (PSi-1) was 400, Mw was 670, and Mw / Mn was 1.68.

To 100 parts by mass of the above-obtained organopolysiloxane (b) (PSi-1) solution (containing silica fine particles (c)), a benzophenone-based ultraviolet absorber (4,6-dibenzoylresorcinol (absorbance A ₂₂₀ : 0. 36 absorbance A ₃₅₀ : 0.074)) was added, and the mixture was aged at 25 ° C. for 24 hours or more. Using 1-butanol and isopropanol as dilution solvents, the non-volatile component is 25% by mass (150 ° C., 45 minutes), the viscosity is 4.4 mPa · s, and the content of the benzophenone-based UV absorber is 0, 5, 10, or 15 A part by weight of an organopolysiloxane (b) (PSi-1) composition solution was prepared. The pH of the composition was stabilized at 5.0.

[3] Preparation of hard coat agent composition 80 parts of an organopolysiloxane (b) composition solution containing organopolysiloxane (b) (PSi-1) obtained in [2] above, obtained in [1] above. 20 parts of a solution containing organopolysiloxane (a) (MSi-1) was mixed to obtain a hard coating composition (HC-1) (I) (4 parts by weight of ultraviolet absorber), (II) (Ultraviolet absorber content 8 parts by mass), (III) (ultraviolet absorber content 12 parts by mass) and (IV) (ultraviolet absorber content 0 parts by mass) were obtained.

[4] Production of resin substrate sample with hard coat layer Using the hard coat agent composition obtained in the above [3], resin substrate samples with a hard coat layer of each example and comparative example were produced as follows. did. In the following sample preparation, a hot-air circulating dryer (manufactured by Sanyo Electric Co., Ltd., CONVECTION OVEN, MOV-202F) was used as a heating and drying means. As the Xe ₂ excimer light irradiation means, an Xe ₂ excimer lamp light source (E500-172, manufactured by Excimer) was used.

[Example 1]
Polycarbonate resin plate (50 mm x 50 mm x 3 mm; Carboglass (registered trademark) polish clear (trade name, manufactured by Asahi Glass Co., Ltd.)) and acrylic primer SHP470 (trade name, manufactured by Momentive Performance Materials, solid content: 10 mass % Solution) is applied by dip method so that the film thickness after drying is 4-5 μm, and is heated and dried for 30 minutes using a hot air circulation dryer set at 120 ° C. to form a primer layer I let you. Next, on this primer layer, the hard coat agent composition (HC-1) (I) was coated by a dip method and held at 25 ° C. for 20 minutes to form an HC-1 coating film.

The resin plate on which the HC-1 coating film is formed is set so that one surface of the coating film faces the position of 1 mm from the Xe ₂ excimer lamp light source (irradiance: 10 mW / cm ² ) in the sealing device. Then, in a nitrogen atmosphere (oxygen concentration: 1% by volume or less), as the Xe ₂ excimer light irradiation treatment, the entire coating film facing the lamp light source is uniformly irradiated with Xe ₂ excimer lamp light for 2 minutes. Was cured. In this example, the heat treatment (first heat treatment) before the Xe ₂ excimer light irradiation treatment was not performed on the resin plate.
Thereafter, the resin plate is taken out from the apparatus and exposed to the atmosphere to be oxidized, and as a heat treatment, a 10 minute heat treatment (second heat treatment) is performed using a hot-air circulating dryer set at 80 ° C. Thus, a resin substrate sample having a hard coat layer was produced.
Incidentally, the illuminance was measured Xe ₂ excimer light illuminance on the surface of the cured film in the Xe ₂ excimer light irradiation treatment is 10mW / cm _^2, Xe ² excimer light irradiation energy received is cured film surface is 1200 mJ / cm ² there were.

The film thickness of the hard coat layer of the resin substrate having the obtained hard coat layer was 2.9 μm. This sample, although the primer layer and the hard coat layer on both surfaces of the polycarbonate plate is formed, only on one side was irradiated with Xe ₂ excimer light, to cure the coating film Xe ₂ excimer light irradiation of the present invention formed A hard coat layer is formed.

[Examples 2-3, 10]
Instead of hard coat agent composition (HC-1) (I), hard coat agent composition (HC-1) (II) (Example 2), hard coat agent composition (HC-1) (III) (Example) 3) or a resin substrate having a hard coat layer with a thickness of 2.9 μm in the same manner as in Example 1 except that the primer layer was coated with the hard coat agent composition (HC-1) (IV) (Example 10). A sample was made. However, in Example 10, the HC-1 coating film was not cured and a hard coat layer was not formed. In each of these examples, the heat treatment (first heat treatment) before the Xe ₂ excimer light irradiation treatment was not performed.

[Example 4]
In place of the hard coat agent composition (HC-1) (I), the hard coat agent composition (HC-1) (IV) is used, and the resin plate on which the HC-1 coating film is formed is heated to 120 ° C. Except that the heat treatment (first heat treatment) for 1 hour was performed using the set hot air circulation dryer, the coating film was cured, and then the Xe ₂ excimer light irradiation treatment was performed. Thus, a resin substrate sample having a hard coat layer with a film thickness of 2.9 μm was produced.

[Examples 5 to 9]
Resin having a hard coat layer with a film thickness of 2.9 μm in the same manner as in Example 4 except that the type of hard coat agent composition (HC-1) and / or the first heat treatment conditions were changed as follows. A substrate sample was prepared.
In Comparative Example 5, the hard coating agent composition (HC-1) (I) was used, and as the first heat treatment, hot air circulation drying set at 120 ° C. on the resin plate on which the HC-1 coating film was formed. Heat treatment was performed for 1 hour using a vessel.
In Comparative Example 6, the hard coat agent composition (HC-1) (I) was used, and as the first heat treatment, hot air circulation drying was set at 120 ° C. on the resin plate on which the HC-1 coating film was formed. Heat treatment was performed for 0.25 hours using a vessel.
In Comparative Example 7, the hard coating agent composition (HC-1) (I) was used, and as the first heat treatment, hot air circulation drying was set at 120 ° C. on the resin plate on which the HC-1 coating film was formed. Heat treatment was performed for 0.5 hour using a vessel.
In Comparative Example 8, the hard coat agent composition (HC-1) (II) was used, and as the first heat treatment, hot air circulation drying set at 120 ° C. on the resin plate on which the HC-1 coating film was formed. Heat treatment was performed for 1 hour using a vessel.
In Comparative Example 9, the hard coat agent composition (HC-1) (III) was used, and as the first heat treatment, hot air circulation drying set at 120 ° C. on the resin plate on which the HC-1 coating film was formed. Heat treatment was performed for 1 hour using a vessel.

[5] Evaluation of Resin Substrate Sample with Hard Coat Layer The following items were evaluated for the resin substrate sample with a hard coat layer obtained in each example of [4] above.

<1> Initial appearance The hard coat layer in the initial state of each sample (excluding Example 10) obtained in [4] above was visually observed and evaluated according to the following criteria.
○ (Correspondence): No crack × (Fail): Crack <2> Scratch resistance Each sample (except Example 10) obtained in the above [4] conforms to JIS K5600 (5.9). , A Taber abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., model: ROTARY ABRASION TESTER) with a wear wheel CALIBRASE (registered trademark) CS-10F (manufactured by TABER) and haze after 500 rotations under a load of 500 g (cloudy The haze difference ΔH ₅₀₀ before and after the test was calculated. The haze was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd., model: HGM-2) in accordance with JIS K7105 (6.4). Judgment criteria are as follows.
○ (Pass): ΔH ₅₀₀ ≦ 5
X (failed): ΔH ₅₀₀ > 5
<3> Hardness of hard coat layer (Martens hardness)
For the hard coat layer surface of each sample obtained in [4] above (excluding Example 10), a Vickers pyramid indenter was attached to a microhardness tester (Fisco Instruments Picodenter HM500), and a load-unloading test. And the load / penetration depth curve was measured. Here, the load speed F was 0.5, 0.1, 0.01 and 0.005 mN / 5 s, the creep C was 5 s, and the unload speed F was the same as the load speed. The measurement data was processed by WIN-HCU (manufactured by Fischer Instruments) to determine Martens hardness HM (N / mm ² ).

  The evaluation results of the initial appearance, scratch resistance, and surface hardness of the hard coat layer obtained above are shown in Table 1 together with the production conditions. Table 1 also shows the evaluation of the possibility of applying the hard coat layer forming step of each example to the continuous coating process.

As is clear from Table 1, a hard coat agent composition containing an ultraviolet absorber having an absorbance at a wavelength of 220 nm of 0.21 or more measured for an acetonitrile solution having a concentration of 0.001% by mass under the condition of an optical path length of 1 cm is used. In the samples of Examples 1 to 3, which were subjected to Xe ₂ excimer light irradiation treatment without first heat treatment to cure the coating film, the samples contained the same UV absorber and the first heat treatment and Xe ₂ excimer light Compared with the samples of Examples 5 to 9 where both treatments of the irradiation treatment were performed, there were no differences in the evaluation results of the initial appearance and scratch resistance, and the same amount of addition of the ultraviolet absorber was also compared in the surface hardness. The case was almost equivalent. In either case, the surface hardness increased with an increase in the addition amount of the ultraviolet absorber. Further, the sample of Example 4 in which both the first heat treatment and the Xe ₂ excimer light irradiation treatment were carried out without containing the ultraviolet absorber had a lower surface hardness than the samples of Examples 1 to 3, and the ultraviolet absorber. In the sample of Example 10 in which only the Xe ₂ excimer light irradiation treatment was performed without containing the coating film, the coating film was not cured.

  From the above results, according to the method for producing a resin substrate with a hard coat layer of the present invention, the initial appearance, scratch resistance, and surface hardness equivalent or higher can be obtained without performing the first essential heat treatment. It turns out that the resin substrate provided with the hard-coat layer which has is obtained. Since the first heat treatment is not required, application to a continuous coating process is possible, and since there is no fear of deterioration of the resin substrate due to the heat treatment, the degree of freedom in selecting the substrate material can be increased.

  The method for producing a resin substrate with a hard coat layer according to the present invention can omit the heat treatment step that has been required in the past, thereby increasing the degree of freedom in selecting productivity and substrate materials. It is useful as a method for producing a resin substrate with a hard coat layer used for vehicle window materials attached to engines, window materials for building materials attached to buildings such as houses and buildings.

Claims (13)

A method for producing a resin substrate with a hard coat layer, comprising a hard coat layer on at least one surface of the resin substrate,
A hard coat agent composition containing an organopolysiloxane and an ultraviolet absorber having an absorbance at a wavelength of 220 nm measured under an optical path length of 1 cm for an acetonitrile solution having a concentration of 0.001% by mass is at least of the resin substrate. Forming a cured film by applying Xe ₂ excimer light irradiation treatment to the coating film in a low oxygen atmosphere after coating on one surface to form a coating film comprising the composition;
A process of oxidizing the cured film and then applying a heat treatment to form a hard coat layer;
The manufacturing method of the resin substrate with a hard-coat layer characterized by comprising. In the cured film formation step, to the coating film before or after applying the Xe ₂ excimer light irradiation treatment, not subjected to a heat treatment method of the hard coat layer with a resin substrate according to claim 1.   The manufacturing method of the resin substrate with a hard-coat layer of Claim 1 or 2 with which the said ultraviolet absorber contains a benzophenone series ultraviolet absorber.   The said ultraviolet absorber is the hard of any one of Claims 1-3 whose light absorbency in wavelength 350nm measured on condition of optical path length 1cm about acetonitrile solution with a density | concentration of 0.001 mass% is 0.1 or more. Manufacturing method of resin substrate with coat layer.   The manufacturing method of the resin substrate with a hard-coat layer of any one of Claims 1-4 whose said low-oxygen atmosphere is an oxygen concentration atmosphere of 5 volume% or less.   The hard coat agent composition according to any one of claims 1 to 5, wherein the hard coat agent composition contains 4 to 20 parts of the ultraviolet absorber with respect to 100 parts by mass of the organopolysiloxane. Manufacturing method of resin substrate.   The manufacturing method of the resin substrate with a hard-coat layer of any one of Claims 1-6 whose heat processing temperature with respect to the cured film after the said oxidation process is below the heat deformation temperature of the said resin substrate.   The process for producing a resin substrate with a hard coat layer according to any one of claims 1 to 6, wherein a heat treatment temperature for the cured film after the oxidation treatment is 50 ° C or more and not more than a heat deformation temperature of the resin substrate. Method. The resin with a hard coat layer according to any one of claims 1 to 8, wherein the Xe ₂ excimer light irradiation treatment is a treatment in which the Xe ₂ excimer light irradiation energy on the cured film surface is 600 to 18000 mJ / cm ^2. A method for manufacturing a substrate.   The method for producing a resin substrate with a hard coat layer according to any one of claims 1 to 9, wherein a ratio of the number of T units in the organopolysiloxane is 70 to 100%.   The hard coat according to any one of claims 1 to 9, wherein the organopolysiloxane is composed of only T units and Q units, and the ratio of the number thereof is T: Q = 90 to 100: 10 to 0. Manufacturing method of resin substrate with layer.   Prior to the coating film forming step, the method further comprises a step of applying a primer composition onto at least one surface of the resin substrate and drying to form a primer layer, and in the coating film forming step, the hard coat agent composition The manufacturing method of the resin substrate with a hard-coat layer of any one of Claims 1-11 which apply | coats a thing on the said primer layer.   The manufacturing method of the resin substrate with a hard-coat layer of any one of Claims 1-12 whose material of the said resin substrate is polycarbonate resin.