JP7669429B2 - Two-part addition curable composition kit and method for producing said composition kit - Google Patents

Description

The present invention relates to a two-part addition curable composition kit that contains a first liquid and a second liquid, and is characterized in that the effect on the curing rate is small even when the first liquid and the second liquid are mixed in any amount, and that abnormalities in the appearance of the cured product due to discoloration of the first liquid during storage and poor curing due to catalyst deactivation in the first liquid are unlikely to occur, and to a method for producing the two-part addition curable composition kit.

It is known that addition-curable compositions for forming release materials such as silicone-based release papers or films can impart properties such as release characteristics, releasability, and water repellency to paper or plastic film substrates by coating the surfaces of various substrates. For example, in protective films and process release films used for surface protection of adhesive surfaces such as pressure-sensitive adhesive sheets and in the manufacture of electronic components such as ceramic capacitors, release properties are imparted to the plastic film by forming a silicone cured coating on the surface of the plastic film substrate.

Silicone-based addition-curable release compositions are broadly divided into solvent-based, solventless, and emulsion-based types, and are usually stored and sold in two- or three-liquid packages. Prior to use, multiple packaged liquids (or emulsions) are mixed, and the resulting composition is coated on the surface of various substrates and cured to form a cured product of the addition-curable composition on the substrate surface, thereby imparting release properties to the substrate surface.

A typical addition-curable composition for release usually contains a polysiloxane containing alkenyl groups as the base agent, an organohydrogenpolysiloxane as the crosslinking agent, a catalyst, an inhibitor, etc. By changing the amount of each component added, the amount of functional groups, the viscosity, the amount applied, etc., it is possible to impart the desired release coating properties to the substrate.

Patent document 1 discloses an addition-curable organopolysiloxane release coating composition. In patent document 1, the coating composition includes A) at least one organopolysiloxane having at least two terminal aliphatically unsaturated groups, B) at least one organopolysiloxane crosslinker having silicon-bonded hydrogen ("Si-H"), where no more than 67 mole percent of the siloxy groups in the organopolysiloxane crosslinker contain Si-H groups, C) at least one hydrosilylation catalyst, and, optionally, D) a hydrosilylation inhibitor.

Such addition curable compositions for release are usually stored and sold as two-part compositions in separate packages.
The most common method for packaging the mixture into two liquids is to package the mixture into (1) a first liquid containing a base agent, a crosslinking agent, and an inhibitor, and a second liquid containing a catalyst, or (2) a first liquid containing a base agent and a catalyst, and a second liquid containing a base agent, a crosslinking agent, and an inhibitor.
In order to obtain the desired curing speed, it is necessary to maintain a constant blend ratio of the catalyst and inhibitor. Therefore, when the above-mentioned (1) packaging method is used, a predetermined amount of the second liquid is mixed with the first liquid before use. When the above-mentioned (2) packaging method is used, the second liquid is mixed with the same amount of the first liquid before use.

The advantage of this type of packaged two-part addition curable composition is that it is an easy-to-understand system for the user. In other words, since the mixing ratio is fixed, it can be used by simply adding a specified number of parts of the second part to the first part, making mixing operations simple. Another advantage is that because the ratio of the base agent to the crosslinking agent is always constant, there is less concern about variations in physical properties due to fluctuations in the amount added.

Patent Document 2 also discloses that a two-liquid addition reaction curing silicone composition can be obtained by mixing two liquids: an emulsion composition containing an alkenyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, and a catalyst activity inhibitor, and a silicone emulsion composition containing a catalyst.

In two-liquid compositions, the catalyst and inhibitor are generally packaged in separate liquids. Inhibitors act like catalyst poisons. For this reason, some components may interact strongly with the catalyst, causing it to lose its catalytic function. If they are not packaged separately, the one-liquid composition will turn black, which may cause abnormalities in the appearance of the product, which is the cured product of the addition curing composition, or cause poor curing.

Special table 2021-500420 Patent Publication No. 2021-24952

Meanwhile, users who use addition curable compositions for peeling have a desire to finely adjust the ratio of the base agent (polysiloxane containing alkenyl groups) and the crosslinking agent (organohydrogenpolysiloxane) to achieve a desired peeling force. In addition, the physical properties of the resulting cured product may vary due to changes in environmental temperature and humidity. In response to this, there is a desire to optimize the physical properties by freely changing the mixing ratio of the two liquids. Thus, there is a need for users to change the mixing ratio of the first liquid and the second liquid when using the composition, while maintaining the curing speed and workable time (pot life), and to change the desired physical properties such as peeling force.
However, in the addition curable peeling composition packaged by the above method (1) or (2), the mixing ratio of the first and second liquids is fixed, and the user cannot adjust the mixing ratio. If the mixing ratio is changed and used, the mixing ratio of the catalyst and inhibitor changes, which causes a problem that the curing speed and pot life during heat curing change.

In light of the above, the objective of the present invention is to provide a two-part addition curable composition kit for peeling that is a two-part type but maintains a constant curing speed and pot life range, allows the mixing ratio to be freely changed during use, and causes minimal abnormalities in the appearance of the cured product.

In order to solve the above problems, the inventors conducted extensive research and discovered that by incorporating an organopolysiloxane having a specific alkenyl group, it is possible to improve the dispersion stability of the platinum complex and significantly prevent strong interactions with inhibitors contained in the same system, and that, while being a two-part type, the mixing ratio can be freely changed during use while maintaining a constant curing speed and pot life range, thereby imparting the desired release coating properties to the substrate and providing a two-part addition curable composition kit for release with minimal abnormalities in appearance in the cured product, thereby completing the present invention.

That is, the present invention provides
A two-part addition curable composition kit comprising a first liquid and a second liquid,
The first liquid is
Component (A): an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals per molecule and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less;
(C) component: an inhibitor;
(D) component: a platinum catalyst;
Component (E): an organopolysiloxane having at least one alkenyl group bonded to a silicon atom in a side chain of the molecular chain, with an alkenyl group content per molecule of 1.0 mmol/g or more and a viscosity at 25°C of 100 mPa·s or more and 100,000 mPa·s or less;
Including,
The first liquid does not contain organohydrogenpolysiloxane,
the amount of the component (E) blended in the first liquid is an amount such that the molar ratio of alkenyl groups in the component (E) to platinum atoms [alkenyl groups in the component (E)/platinum] is 50 or more and 1,000 or less;
The second liquid is
Component (B): An organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in each molecule,
the second liquid does not contain the component (A), the component (C), the component (D), or the component (E);
An addition curable composition can be obtained by mixing the first liquid and the second liquid.
The present invention relates to a two-part addition curable composition kit.
Component (C) may be an alkynol compound, since this is easily dispersed in the organopolysiloxane composition and is less likely to precipitate.
Component (D) may be a platinum vinyl siloxane complex, since this has good compatibility with components (A) and (E) and allows for stable dispersion.

In the two-liquid addition curable composition kit having the above-mentioned configuration of the present invention, the platinum catalyst (D) containing a platinum complex and the inhibitor (C) are coordinated in a thread-like shape by the organopolysiloxane having a specific alkenyl group (E) to improve the dispersion stability of the platinum complex, and the steric hindrance of the organopolysiloxane molecule having an alkenyl group (E) in the thread-like shape significantly prevents strong interaction between the platinum complex (D) and the inhibitor (C), and is believed to achieve the effects of the present invention. This makes it possible to suppress strong interaction between the platinum complex (D) and the inhibitor (C), and reduces discoloration of the first liquid during storage. As a result, it is possible to suppress abnormal appearance in the cured product of the addition curable composition obtained by mixing the first liquid and the second liquid. In addition, the deactivation of the catalyst (D) contained in the first liquid is suppressed, and as a result, poor curing of the cured product is less likely to occur. Furthermore, the two-liquid addition curable composition kit obtained by this blending contains the inhibitor (C) and the platinum catalyst (D) in the same liquid. This makes it possible to adjust the mixing ratio of the alkenyl-containing organopolysiloxane contained in the first liquid and the organohydrogenpolysiloxane (B), which is contained in the second liquid, to the desired ratio during use, and also provides the effect of maintaining the curing speed and pot life within a certain range.

Therefore, the two-part addition curable composition kit of the present invention is a two-part type, but while maintaining a certain range of curing speed and pot life, it is possible to change the mixing ratio of the first and second parts within a specified range, and thus it is possible to impart the desired peel-off coating properties to the substrate, and is also characterized by being less prone to abnormalities in the appearance of the cured product.

The following describes in detail the two-part addition curable composition kit, the method for producing the composition kit, and the release paper formed using the composition kit, according to the present invention. For convenience, the combination of the "first liquid" and the "second liquid" may also be referred to as the "two-part addition curable composition" in this specification.

The two-part addition curable composition kit according to the present invention comprises:
A two-part addition curable composition kit comprising a first liquid and a second liquid,
The first liquid is
Component (A): an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals per molecule and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less;
(C) component: an inhibitor;
(D) component: a platinum catalyst;
Component (E): an organopolysiloxane having at least one alkenyl group bonded to a silicon atom in a side chain of the molecular chain, with an alkenyl group content per molecule of 1.0 mmol/g or more and a viscosity at 25°C of 100 mPa·s or more and 100,000 mPa·s or less;
Including,
The first liquid does not contain organohydrogenpolysiloxane,
the amount of the component (E) blended in the first liquid is an amount such that the molar ratio of alkenyl groups in the component (E) to platinum atoms [alkenyl groups in the component (E)/platinum] is 50 or more and 1,000 or less;
The second liquid is
(B) Component: An organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in each molecule,
the second liquid does not contain the component (A), the component (C), the component (D), or the component (E);
An addition curable composition can be obtained by mixing the first liquid and the second liquid.
It is characterized by:

The two-part addition curable composition kit of the present invention is a kit that has at least two types of liquid compositions, a first part and a second part, which can be mixed to obtain an addition curable composition.
In addition to the first and second liquids, a third liquid containing neither a catalyst nor an inhibitor may be further combined.
The above-mentioned two-liquid addition curable composition kit may be any one that ultimately contains the first liquid and the second liquid, and either or both of the first liquid and the second liquid may be packaged separately depending on circumstances such as storage, transportation, etc. For example, the first liquid may be packaged separately into a first pre-mixed liquid containing the components (C) and (E) and a second pre-mixed liquid containing the components (D) and (E) and stored, and the first pre-mixed liquid and the second pre-mixed liquid may be mixed together to obtain the first liquid before mixing with the second liquid.

(式(1)中、R¹は、互いに独立に、水酸基又は炭素数1～12の1価炭化水素基であり、当該1価炭化水素基は、置換又は非置換の、脂肪族不飽和結合を有さない、1価炭化水素基であり、R¹¹は炭素数2～10のアルケニル基であり、aは2以上の整数であり、bは1以上の整数であり、cは0以上の整数であり、dは0以上の整数である。
a+b+c+dは上記の粘度範囲を満たす数値であれば特に限定されず、10以上3,000以下であっても良いが、20以上2000以下であると好ましく、50以上1000以下であるとより好ましい。) (Component (A))
The first liquid may further contain, as component (A), an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals per molecule and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less, and the second liquid may not contain the above-mentioned (A).
Component (A) is a crosslinking component that, together with component (B) described below, forms a cured product through an addition curing reaction between SiH groups and alkenyl groups. Component (A) is an organopolysiloxane whose average compositional formula is represented by general formula (1) and which has two or more alkenyl groups bonded to silicon atoms per molecule, only at the molecular chain terminals.
Hereinafter, the organopolysiloxane of component (A) will also be referred to as the alkenylorganopolysiloxane of component (A).

(In formula (1), R ¹ 's are each independently a hydroxyl group or a monovalent hydrocarbon group having 1 to 12 carbon atoms, which is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bonds; R ¹¹ is an alkenyl group having 2 to 10 carbon atoms; a is an integer of 2 or greater, b is an integer of 1 or greater, c is an integer of 0 or greater, and d is an integer of 0 or greater.
a+b+c+d is not particularly limited as long as it satisfies the above viscosity range, and may be 10 or more and 3,000 or less, but is preferably 20 or more and 2000 or less, and more preferably 50 or more and 1000 or less.

Examples of the alkenyl group ^R11 in component (A) include alkenyl groups having 2 to 8 carbon atoms, such as vinyl, allyl, 1-butenyl, and 1-hexenyl groups, with vinyl and allyl being preferred, and vinyl being particularly preferred. These alkenyl groups react with component (B), described below, to form a network structure. The alkenylorganopolysiloxane, which is component (A), has an average of about 2 alkenyl groups, preferably 1.6 to 2.2 alkenyl groups in its molecule.

When R ¹ bonded to a silicon atom in component (A) is a monovalent hydrocarbon group, specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, xylyl, biphenyl, and naphthyl; benzyl and substituted hydrocarbon groups in which some or all of the hydrogen atoms in these hydrocarbon groups have been substituted with halogen atoms, cyano groups, etc., such as a chloromethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group, a 3-chloropropyl group, a chlorophenyl group, a dibromophenyl group, a tetrachlorophenyl group, a difluorophenyl group, a β-cyanoethyl group, a γ-cyanopropyl group, a β-cyanopropyl group, etc. Particularly preferred monovalent hydrocarbon groups are a methyl group and a phenyl group.

The alkenylorganopolysiloxane of component (A) may be linear or branched, or may be a mixture of these.

Component (A) may further contain a -SiOH group at part of the molecular chain terminal. In this case, the ratio of the number of silicon atoms having an OH group to the total number of terminal silicon atoms of all organopolysiloxanes in component (A) is less than 5%, and preferably less than 2%. If this ratio satisfies the above condition, the addition polymerization will proceed sufficiently and a sufficient cured coating can be obtained.

The viscosity of the alkenylorganopolysiloxane of component (A) at 25°C is from 10 mPa·s to 1,000,000 mPa·s, preferably from 20 mPa·s to 500,000 mPa·s, and more preferably from 50 mPa·s to 50,000 mPa·s. If the viscosity of component (A) is too low, it is prone to volatilization and the formulation is prone to become unstable. If the viscosity of component (A) is too high, the resulting silicone composition is likely to be significantly lacking in fluidity, and there is a risk of reduced application workability. Furthermore, when emulsifying, the dispersion and emulsifying properties of the composition when mechanically stirred are reduced, which may result in poor emulsification.

Furthermore, in order to adjust the final physical properties of the cured coating and to adjust the viscosity during emulsification, component (A) can also contain two or more types of alkenyl-containing organopolysiloxanes with different viscosities.
In this specification, the viscosity is the absolute viscosity value measured by a Brookfield type rotational viscometer at 25° C. (the same applies hereinafter in this specification).

The alkenylorganopolysiloxane of component (A) can be produced by methods known to those skilled in the art. For example, it can be produced by condensation and/or ring-opening polymerization of linear and/or cyclic low molecular weight siloxanes using acid catalysts such as sulfuric acid, hydrochloric acid, nitric acid, activated clay, and tris(2-chloroethyl)phosphite, or base catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-butylphosphonium hydroxide, sodium silanolate, and potassium silanolate.

The amount of component (A) blended is preferably 5 parts by mass or more and 95 parts by mass or less, more preferably 50 parts by mass or more and 90 parts by mass or less, and even more preferably 60 parts by mass or more and 85 parts by mass or less, assuming the solid content in the first liquid to be 100 parts by mass.
The solid content here means the total amount of components excluding water (the same applies hereinafter in this specification).

(Component (B))
The component (B) in the present invention is an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in each molecule, and is a crosslinking component that forms a cured product through an addition curing reaction between SiH groups and alkenyl groups.

(式(2)中、R²は、互いに独立に、水素原子、水酸基又は、置換又は非置換の炭素数1～12の1価炭化水素基である。但し、1分子中にケイ素原子と結合した水素原子を2個以上含有し、aは2以上の整数であり、bは1以上の整数であり、cは0以上の整数であり、dは0以上の整数である。
a+b+c+dは後述する粘度範囲を満たす数値であれば特に限定されず、5以上600以下であってもいが、10以上400以下であっても良い。) The organohydrogenpolysiloxane of component (B) is represented by the following average composition formula (2).

(In formula (2), R ² are each independently a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, provided that each molecule contains two or more hydrogen atoms bonded to silicon atoms, a is an integer of 2 or more, b is an integer of 1 or more, c is an integer of 0 or more, and d is an integer of 0 or more.
a+b+c+d is not particularly limited as long as it satisfies the viscosity range described below, and may be 5 or more and 600 or less, or 10 or more and 400 or less.

The viscosity of component (B) at 25°C may be from 1 mPa·s to 3,000 mPa·s, and preferably from 10 mPa·s to 1,000 mPa·s. If the viscosity of component (B) is within the above range, it is possible to suppress the phenomenon in which component (B) volatilizes before the curing reaction with the alkenyl groups in components (A) and (E) has sufficiently progressed, or the curing property deteriorates due to low reactivity with the alkenyl groups in components (A) and (E).

When ^R2 bonded to a silicon atom in component (B) is another monovalent hydrocarbon group, specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, xylyl, biphenyl, and naphthyl; and benzene. and substituted hydrocarbon groups in which some or all of the hydrogen atoms in these hydrocarbon groups have been substituted with halogen atoms, cyano groups, etc., such as a chloromethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group, a 3-chloropropyl group, a chlorophenyl group, a dibromophenyl group, a tetrachlorophenyl group, a difluorophenyl group, a β-cyanoethyl group, a γ-cyanopropyl group, a β-cyanopropyl group, etc. Particularly preferred monovalent hydrocarbon groups are a methyl group and a phenyl group.

The amount of component (B) in the composition of the present invention is determined according to the amount of alkenyl in components (A) and (E). For example, when the ratio of the number of alkenyl groups (NA) bonded to silicon atoms in components (A) and (E) to the number of hydrogen atoms (NH) bonded to silicon atoms contained in component (B) is expressed as (NH/NA) (hereinafter referred to as "hydrogen-alkenyl ratio (NH/NA)"), the amount of component (B) may be an amount that satisfies 1.0≦(NH/NA)≦6.0, and preferably an amount that satisfies 1.3≦(NH/NA)≦4.0. If the amount of component (B) is such that the ratio falls within the above range, a good cured coating can be obtained in which the release force is stable and the release agent does not migrate to the target material.
Generally, when the above ratio (NH/NA) exceeds the above range, the amount of unreacted SiH groups remaining in the cured product increases, which not only causes a significant increase in peel strength, but also tends to increase variation in peel strength due to interaction with the adhesive.
Like component (A), component (B) can also be produced by a method known to those skilled in the art.

Component (B) may further contain a -SiOH group at part of the molecular chain terminal. In this case, the ratio of the number of silicon atoms having an OH group to the total number of terminal silicon atoms of all organopolysiloxanes in component (B) is less than 5%, and preferably less than 2%. If this ratio satisfies the above condition, the addition polymerization will proceed sufficiently and a sufficient cured coating can be obtained.

In the present invention, components (A), (B), and (E) described below may further contain octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6). The total mass of components D4, D5, and D6 is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less, and even more preferably 500 mass ppm or less, relative to the total mass of components (A), (B), and (E). If the total mass of the components satisfies the above conditions, the storage stability and emulsion stability of each liquid in the composition of the present invention obtained will be further improved.

(Component (C))
The component (C) in the present invention is an inhibitor, and in particular the component (C) is a hydrosilylation reaction inhibitor. The inhibitor (C) can be used to adjust the curing speed and workable time (pot life) during heat curing of the composition.
Examples of the inhibitor as component (C) include alkynols (i.e., acetylenic alcohols), ketones, enyne compounds, organic phosphorus compounds, and organic nitrogen compounds. Specific examples of alkynols include methylbutynol, dimethylhexynol, ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 1-propyn-3-ol, 1-butyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, and 4-ethyl-1-octyn-3-ol. Specific examples of enyne compounds include 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne. Specific examples of component (C) include maleates (e.g., diallyl maleate, bismaleate, or n-propyl maleate). These inhibitors can be used alone or in combination of two or more.

In particular, alkynol compounds are preferred as component (C). This is because alkynol compounds are liquid in the temperature range in which they are generally used and do not precipitate easily, are easily dispersed in the first liquid, and can maintain a good dispersed state even after mixing with the second liquid, making them preferable. There are no particular restrictions, but ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 4-ethyl-1-octyn-3-ol, etc. are preferred.

The amount of hydrosilylation inhibitor in component (C) can be appropriately selected taking into consideration the type of hydrosilylation inhibitor, the characteristics and amount of hydrosilylation catalyst, the amount of alkenyl groups in components (A) and (E), and the amount of silicon-bonded hydrogen atoms in component (B), but is usually in the range of 0.001 to 2.0 parts by mass, and preferably 0.01 to 1.5 parts by mass, assuming that the solid content in liquid 1 is 100 parts by mass.

(Component (D))
Component (D) can be used as a hydrosilylation catalyst and is a platinum catalyst. (D) Platinum catalysts are highly reactive and are suitable. Examples of _platinum compounds that can be used as platinum catalysts include _platinum halides (e.g., _PtCl4 , _H2PtCl4.6H2O , _{NA2PtCl4.4H2O , H2PtCl4.6H2O} , _{etc. ) .} O and cyclohexane), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes (e.g., platinum-1,3-divinyl 1,1,3,3-tetramethyldisiloxane complexes), bis-(γ-picoline)-platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride), bis(alkynyl)bis(triphenylphosphine)platinum complexes, bis(alkynyl)(cyclooctadiene)platinum complexes, etc. Also, the hydrosilylation catalyst as the platinum catalyst can be used in a microencapsulated form. In this case, for example, a thermoplastic resin (e.g., polyester resin or silicone resin) can be used to form a fine particle solid that contains the catalyst and is insoluble in the polyorganosiloxane. The platinum catalyst can also be used in the form of an inclusion compound, for example, by being enclosed (inclosed) in cyclodextrin. It can also be fixed to a fine particle carrier material (e.g., activated carbon, aluminum oxide, silicon oxide).

In particular, platinum-vinylsiloxane complexes are suitable as component (D) in the present invention. (An example of a platinum-vinylsiloxane complex is platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.) Such platinum-vinylsiloxane complexes have good compatibility with the organopolysiloxanes of components (A) and (E), and can be dispersed stably.

The amount of component (D) used is an effective amount according to the desired curing temperature and curing time depending on the application, but usually the concentration of the catalytic metal element relative to the total mass of the first liquid (first liquid containing water in the case of an emulsion-type composition) is preferably in the range of 0.5 to 1,000 ppm by mass, more preferably 1 to 500 ppm by mass, and even more preferably 5 to 200 ppm by mass. If the amount is less than 0.5 ppm by mass, the addition reaction will be significantly slower. On the other hand, if the amount exceeds 1,000 ppm by mass, the cost will increase and it is economically undesirable.

In addition to the platinum catalyst of component (D), a platinum group catalyst may also be used in combination. Platinum group catalysts that can be used in combination with component (D) consist of platinum group metals or compounds containing these metals. Examples of metals that make up platinum group catalysts include rhodium, palladium, ruthenium, and iridium, and catalyst compounds containing these metals can be used.

(式(3)中、R³は、互いに独立に、水酸基、置換又は非置換の炭素数1～12の1価炭化水素基、または置換又は非置換の炭素数2～10のアルケニル基である。但し、R³の少なくとも1つは炭素数2～10のアルケニル基であり、分子鎖側鎖にケイ素原子と結合したアルケニル基を少なくとも1個以上有する。aは2以上の整数であり、bは1以上の整数であり、cは0以上の整数であり、dは0以上の整数である。
a+b+c+dは上記の粘度範囲を満たす数値であれば特に限定されず、80以上1,500以下であっても良いが、100以上1200以下であっても良く、150以上1000以下であっても良い。)
また、一般式(3)で表されるアルケニルオルガノポリシロキサンは、分子1個当たり平均して少なくとも3個のアルケニル基を有することが好ましい。 (Component (E))
Component (E) in the present invention is an organopolysiloxane that has at least one alkenyl group bonded to a silicon atom in a side chain on the molecular chain and has a viscosity of 100 mPa·s or more and 100,000 mPa·s or less at 25° C. The viscosity of component (E) is more preferably in the range of 150 to 80,000 mPa·s, and particularly preferably 200 to 50,000 mPa·s.
The amount blended in the composition is an amount such that the molar ratio of alkenyl groups in component (E) to platinum atoms [alkenyl groups in component (E)/platinum] is 50 or more and 1,000 or less.
The component (E) can also be represented by the following general formula (3).

(In formula (3), ^R3 's are each independently a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, with the proviso that at least one ^R3 is an alkenyl group having 2 to 10 carbon atoms and has at least one alkenyl group bonded to a silicon atom on a side chain of the molecular chain. a is an integer of 2 or greater, b is an integer of 1 or greater, c is an integer of 0 or greater, and d is an integer of 0 or greater.
a+b+c+d is not particularly limited as long as it satisfies the above viscosity range, and may be 80 or more and 1,500 or less, 100 or more and 1200 or less, or 150 or more and 1000 or less.
Furthermore, the alkenylorganopolysiloxane represented by general formula (3) preferably has an average of at least three alkenyl groups per molecule.

Examples of the alkenyl group in component (E) include alkenyl groups having 2 to 10 carbon atoms, such as vinyl groups, allyl groups, 1-butenyl groups, and 1-hexenyl groups, with vinyl groups and allyl groups being preferred, and vinyl groups being particularly preferred. These alkenyl groups react with component (B) to form a network structure.

The number of alkenyl groups in one molecule is not particularly limited as long as there is one or more on the molecular chain side chain, but it is preferable that there are three or more in the molecule of component (E) and that the alkenyl group content per molecule is 1.0 mmol/g or more. There is no particular upper limit to the alkenyl group content, but if it is 1.0 mmol/g or more and 5.0 mmol/g or less, the crosslink density is not too high, and it is preferable. At least one such alkenyl group is bonded to a silicon atom on the molecular chain side chain, and other alkenyl groups may be bonded to silicon atoms at the terminals of the molecular chain or may be bonded to silicon atoms on the molecular chain side chains.

Other monovalent hydrocarbon groups bonded to silicon atoms in component (E) are specifically alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, xylyl, biphenyl, and naphthyl; benzyl aryl groups, phenylethyl groups, phenylpropyl groups, methylbenzyl groups, and other aralkyl groups; and substituted hydrocarbon groups in which some or all of the hydrogen atoms in these hydrocarbon groups have been replaced with halogen atoms, cyano groups, and the like, such as chloromethyl groups, 2-bromoethyl groups, 3,3,3-trifluoropropyl groups, 3-chloropropyl groups, chlorophenyl groups, dibromophenyl groups, tetrachlorophenyl groups, difluorophenyl groups, β-cyanoethyl groups, γ-cyanopropyl groups, and β-cyanopropyl groups. Particularly preferred monovalent hydrocarbon groups are methyl groups and phenyl groups.

The alkenylorganopolysiloxane of component (E) may be linear or branched, or may be a mixture of these.

Component (E) may further contain one having a -SiOH group at part of the molecular chain terminal. In this case, the ratio of the number of silicon atoms having an OH group to the total number of terminal silicon atoms of all organopolysiloxanes in component (E) is less than 5%, and preferably less than 2%. If this ratio satisfies the above condition, addition polymerization will proceed sufficiently and heavy peeling can be suppressed.

The alkenylorganopolysiloxane of component (E) can be produced by methods known to those skilled in the art. For example, it can be produced by condensation and/or ring-opening polymerization of linear and/or cyclic low molecular weight siloxanes using acid catalysts such as sulfuric acid, hydrochloric acid, nitric acid, activated clay, and tris(2-chloroethyl)phosphite, or base catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-butylphosphonium hydroxide, sodium silanolate, and potassium silanolate.

As described above, the amount of component (E) is such that the ratio of alkenyl groups in component (E) to platinum atoms contained in the first liquid [alkenyl groups in component (E) (mol)/platinum atoms (mol)] is from 50 to 1,000, preferably from 70 to 800, more preferably from 80 to 500, and even more preferably from 100 to 400. Adding component (E) in an amount that satisfies the above ratio within this range prevents deactivation of the platinum catalyst and has little effect on the physical properties of the cured coating.
For example, if 10 parts by mass of component (E) with a molecular weight of 1000 containing 10 alkenyl groups in the molecule is blended into 100 parts by mass of the first liquid, and the platinum atomic weight in the first liquid is 1.0× ^10-3 mol, [alkenyl groups (mol) in component (E)]/[platinum atoms (mol)] is [10×10/1000 (mol)]/[1.0× ^10-3 (mol)] = 100.

(Component (F))
The first and second liquids of the two-liquid addition curable composition kit of the present invention may be of a solventless type or an emulsion type obtained by emulsifying them.
In the case of the emulsion type, the first liquid and the second liquid each further contain an emulsifier as the component (F) and water as the component (G).
As the emulsifier for component (F), a nonionic surfactant or a protective colloid is particularly suitable. When a protective colloid is used as component (F), the emulsion stability is high and a release coating having a more stable release force after curing can be obtained.

When an ionic surfactant such as a cationic or anionic surfactant is used as the emulsifier of component (F), the emulsifier remaining on the film surface may adhere to electronic components and affect their performance (e.g., the occurrence of a charge-up phenomenon). For this reason, when applying the two-part addition curable peeling composition kit of the present invention to a release film used for electronic components, it is particularly suitable to use a protective colloid with low ionicity such as polyvinyl alcohol or a nonionic surfactant.

Examples of the protective colloid of component (F) include polymeric compounds such as unmodified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, ethylene-modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, and polycarboxylic acid, as well as alkali metal salts and/or ammonium salts thereof. In order to suppress the above-mentioned charge-up phenomenon, unmodified polyvinyl alcohol, which has low ionicity, is particularly preferred.

The HLB value, which indicates the balance between hydrophilicity and lipophilicity, of the nonionic surfactant used as component (F) may be 8.0 to 19.0, preferably 10.0 to 18.0, and more preferably 10.0 to 16.0. If a nonionic surfactant with an HLB value within the above range is used, storage stability and dilution stability tend to be improved. Note that surfactants with low HLB values may be used in combination as other emulsifying aids.

Examples of such nonionic surfactants include sorbitan fatty acid esters, glycerin fatty acid esters, decaglycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol pentaerythritol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene alkylamine fatty acid amides, polyalkyl glycosides, and the like. These nonionic surfactants are also preferred in terms of safety, stability, and cost. In particular, polyoxyethylene alkyl ethers are preferred from the viewpoint of emulsion stability. The nonionic surfactants can be used alone or in combination of two or more kinds.

When the first and second liquids of the two-part addition curable composition kit of the present invention are emulsion type, the content of component (F) in the first and second liquids is preferably 1 to 10 parts by mass. If it is less than 1 part by mass, emulsification is difficult, and if it exceeds 10 parts by mass, the viscosity of the aqueous emulsion composition increases, making it difficult to handle. The content of component (F) is more preferably 3 to 6 parts by mass.

(Component (G))
Component (G) is water. Although not particularly limited, it is preferable to use ion-exchanged water. The pH of the ion-exchanged water is preferably pH 2.0 to 12.0, particularly preferably pH 4.0 to 10.0. The use of mineral water is not recommended, but if it is used, it is preferably used in combination with a metal deactivator or the like. The amount of water added as component (G) used during emulsification is 20 to 80 parts by mass, preferably 35 to 70 parts by mass, based on 100 parts by mass of the entire two-part addition curable composition of the present invention.

When the two-part addition curable composition of the present invention is an emulsion type composition, the composition is stable against dilution with water and can be further diluted after preparation. There is no particular limit to the amount of water (dilution water) used for dilution. When the solid content of the composition is high, there is a tendency for it to be less repellent when applied to a substrate, and when the solid content is low, there is a tendency for it to be easier to obtain a good coating appearance in the peelable coating film after curing. Therefore, the amount of dilution water can be determined according to the balance of these physical properties. When the two-part addition curable composition of the present invention is an oil-in-water silicone emulsion, the composition is a water-solvent system, which is preferable in that it is more environmentally friendly than systems that use organic solvents.

When the two-part addition curable composition of the present invention is an emulsion type, the emulsion can be produced by mixing and emulsifying the above components using a commonly used mixer suitable for producing emulsions, such as a homogenizer, colloid mill, homomixer, or high-speed stator rotor stirrer. The emulsion can be produced by mixing and stirring component (A) or component (B), component (F), and all or part of the water (G) to prepare a water-in-oil emulsion, and then adding the remaining water and stirring to produce an oil-in-water emulsion. This method of first producing a water-in-oil emulsion and then producing an oil-in-water emulsion is preferred in terms of ease of adjusting the emulsion particle size and emulsion stability.

When the two-part addition curable composition of the present invention is an emulsion type, a preservative may be blended into the first part. Preservatives are mainly used to prevent the proliferation and growth of bacteria and fungi and to maintain quality. There are no particular limitations on the preservative, and existing preservatives can be used. In particular, preservatives approved as food additives and preservatives with a long history of use are considered to have low toxicity to the human body within the upper limit of the allowable blending amount, and therefore can be used preferably. Specific preservatives include benzoic acid, sodium benzoate, paraben, salicylic acid, sodium salicylate, sorbic acid, potassium sorbate, and phenoxyethanol.

In addition, when the two-liquid addition curing composition of the present invention is an emulsion type, a pH adjuster may be blended in the second liquid. The pH adjuster is used to maintain the pH of the coating material in a desired pH range and maintain the quality. As the pH adjuster, acids, bases, salts, or buffers combining these can be used depending on the purpose. Existing pH adjusters can be used, but components that are catalyst poisons are not suitable. For example, compounds containing nitrogen such as amines and azo compounds, and other compounds containing sulfur, tin, phosphorus, etc. are not suitable as additives for addition curing systems when used as pH adjusters. In the composition of the present invention, since the pH adjuster is applied to the second liquid containing organohydrogenpolysiloxane, it is preferable to use an acid or an acid salt as the pH adjuster. Examples include malic acid, lactic acid, acetic acid, adipic acid, citric acid, and tartaric acid.

(Method of manufacturing two-part addition curable composition kit)
The two-part addition curable composition kit of the present invention comprises:
a base compounding step of compounding component (A) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals per molecule and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less;
a catalyst protection step of mixing the component (E) and the component (D) to obtain a protected catalyst;
a step of producing a protected catalyst composition, comprising mixing the protected catalyst with the component (C) to obtain a first liquid which is a protected catalyst composition;
A first liquid manufacturing process including the steps of:
A two-part addition curable composition kit having the first liquid and the second liquid can be produced by a production method including a second liquid production step of producing a second liquid containing the above-mentioned component (B).

Specifically, for example, the first liquid can be prepared by mixing the (E) component and the (D) component using a stirrer such as a planetary mixer or a console mixer to obtain a protected catalyst through a catalyst protection step, and then mixing the (C) component and the protected catalyst using a stirrer such as a planetary mixer or a console mixer to obtain a protected catalyst composition production step. The base compounding step can be performed at any timing, and the protected catalyst can be mixed with the (A) component (the catalyst protection step is performed after the base compounding step), the base compounding step can be performed after the catalyst protection step, or the base compounding step can be performed after the protected catalyst composition production step.
The protected catalyst in this specification is a catalyst in a state in which the component (E) is coordinated to surround the platinum catalyst of the component (D) in a thread-like manner, and is considered to be capable of suppressing the strong interaction between the inhibitor of the component (C) and the platinum catalyst of the component (D) while improving the dispersion stability of the platinum catalyst of the component (D). Therefore, the protected catalyst composition obtained through the first liquid production process contains the above-mentioned component (E), the above-mentioned component (D), and the above-mentioned component (C).
The second liquid can also be prepared by mixing one or more components (B) using a similar mixer.

The two-part addition curable composition of the present invention can also be an emulsion-type two-part addition curable composition.
A method for producing such an emulsion-type two-liquid addition curable composition kit includes, for example, the following steps:
a base compounding step of compounding component (A) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals per molecule and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less;
a catalyst protection step in which the component (E) and the component (D) are mixed using a stirrer such as a planetary mixer or a console mixer to obtain a protected catalyst, a protected catalyst composition production step in which the component (C) and the protected catalyst are mixed using a stirrer such as a planetary mixer or a console mixer to obtain a protected catalyst composition, and a first liquid emulsification step in which the component (F) and water (component (G)) are added to the protected catalyst composition to obtain a first emulsion;
and a second emulsification step of obtaining a second emulsion containing the component (B), the component (F), and the component (G).
In the first emulsification step, emulsification can be performed by a phase inversion method using a stirring device capable of high shear, such as a high-speed stirrer typified by a planetary mixer or homomixer, an ultrasonic homogenizer, or a high-pressure homogenizer. As described above, the (F) and (G) components may be added in their entirety at once, or a method may be used in which a portion of the components is added and mixed first to adjust the emulsion, and then the remainder is added and mixed to cause phase inversion. Alternatively, an appropriate amount may be left as the remainder, and this (G) component may be added last to dilute and adjust.
For the second emulsification step, a similar mixer may be used to first add one or more of the (B) component, the (F) component, and a portion of the (G) component, mix and emulsify, and then add the remaining (G) component later to dilute and adjust. Although not specified in the respective explanations, each component may be used alone or in combination of two or more types.

The present invention also provides a release material, such as a release paper or film, which comprises a thin-layer substrate such as paper or plastic, and a cured coating formed by curing the two-part addition curable composition of the present invention. The substrate material in the release material of the present invention is not particularly limited, and may be paper, plastic, glass, metal, cloth, etc.
Examples of the paper include fine paper, coated paper, art paper, glassine paper, polyethylene laminated paper, craft paper, Japanese paper, and synthetic paper.

Examples of plastic materials include polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polyester, polyimide, polyamide, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polytetrafluoroethylene, polystyrene, polymethylpentene, ionomer, polyacrylic acid ester, polymethacrylic acid ester, nylon ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, triacetyl cellulose, polyether ether ketone, polyether sulfine, polyphenylene sulfide, polyurethane, polyether imide, modified polyphenylene ether, polyether ether ketone, polyacrylonitrile, norbornene, cycloolefin, cellophane, and the like.
There is no particular limitation on the type of glass, and glass that has been subjected to chemical strengthening treatment, etc. Glass fiber can also be used, and the glass fiber may be used alone or in combination with other resins.
Examples of metals include aluminum foil, copper foil, gold foil, silver foil, and nickel foil.
The thin layer substrate in the present invention can be used as a release material used in protective films for pressure sensitive adhesive sheets, release films for electronic component manufacturing processes, etc. Therefore, there are no particular limitations on the thickness thereof as long as it is the thickness of a thin layer material usually used for these applications.

In the two-liquid addition curable composition kit of the present invention, the first liquid and the second liquid can be mixed in a desired mixing ratio. There are no particular limitations, but as mentioned above, the ratio between the number of alkenyl groups (NA) bonded to silicon atoms in the (A) and (E) components in the first liquid and the number of hydrogen atoms (NH) bonded to silicon atoms contained in the (B) component in the second liquid can be adjusted within an amount range such that the hydrogen-alkenyl ratio (NH/NA) defined above satisfies 1.0≦(NH/NA)≦6.0, and preferably satisfies 1.3≦(NH/NA)≦4.0.

The two-part addition curable composition kit of the present invention may be applied to a substrate by a known method after mixing the first and second liquids (after mixing the first and second emulsions in the case of an emulsion-type two-part addition curable composition kit). Depending on the application, the two-part addition curable composition may be applied to one side or both sides of the substrate. Known application methods include, for example, roll coating, reverse roll coating, gravure coating, reverse gravure coating, brush coating, spray coating, air knife coating, immersion, bar coat coating, spin coat coating, blade coating, gate roll coating, and meniscus coating.

In the present invention, the thickness of the coating film after the two-part addition curable composition is applied to a substrate and dried is not particularly limited, but may be, for example, 0.01 to 1 μm. From the viewpoint of improving transparency and reducing costs by reducing the thickness of the coating film, the thickness of the coating film is preferably 0.01 to 0.5 μm, and particularly preferably 0.01 to 0.3 μm.

The two-part addition curable composition of the present invention is applied to a substrate, dried, and forms a release coating on the substrate as the curing reaction proceeds. The curing reaction can be carried out at room temperature (e.g., 25°C), but it is also possible to accelerate the curing reaction by heating for a few seconds to a few hours. The heating temperature for effect acceleration is not particularly limited, and can be, for example, 70°C or higher. The upper limit of the heating temperature can be determined according to the thermal decomposition temperature of the organopolysiloxane, and can be, for example, 250°C or lower. The upper limit of the heating temperature can be determined according to the heat resistance temperature of the substrate, and can be, for example, 150°C or 100°C. The curing reaction acceleration treatment by heating can be carried out by a conventional method such as a heating roll, a heating drum, or a hot air drying oven.

The present invention will now be described with reference to examples. However, the present invention is not limited to these examples. In these examples, reactions and treatments were carried out at room temperature (23°C) and atmospheric pressure unless otherwise specified. Furthermore, amounts, parts, percentages, etc. are by weight unless otherwise specified.

(Method for preparing two-part addition curable composition kit)
As shown in the table below, the first and second parts of a two-part addition curable composition kit were prepared. As a preparation example, Example 1 is described below. Other examples and comparative examples were prepared in the same manner.

Example 1
First liquid: First, 50.0 parts by mass of polydimethylsiloxane containing alkenyl groups only at the molecular chain terminals, with both ends blocked with dimethylvinylsilyl groups and a viscosity of 1000 mPa·s as component (A), 0.09 parts by mass of 1-ethynyl-1-cyclohexanol (manufactured by Nissin Chemical Industry Co., Ltd.) as component (C), 0.35 parts by mass of a platinum-vinylsiloxane complex solution (platinum content: 100 ppm/g) as component (D), and 0.5 parts by mass of a dimethylvinylsiloxane complex solution containing alkenyl groups at both ends and in the side chains and with a viscosity of 600 1.0 part by mass of an alkenyl-containing polydimethylsiloxane (alkenyl content: 1.7 mmol/g) having a viscosity of mPa·s, 0.1 part by mass of sorbic acid as a preservative, and 6.5 parts by mass of a nonionic surfactant (Pegnol T10/80 manufactured by Toho Chemical Industry Co., Ltd.) as component (F) were added and mixed, and purified water was added as component (G) so that the total parts by mass of the first liquid was 100 parts by mass, and the first liquid was prepared by stirring at 4000 rpm using an Ultra Turrax T50 Basic Shaft Generator G45M manufactured by IKA. The platinum content was blended so that [alkenyl group (mol) in component (E) / platinum atom (mol)] was 104. Silicone emulsion (I) was prepared by the above process.

Liquid 2: First, 35.0 parts by mass of methylhydrogenpolysiloxane (B) with SiH groups on the side chains and both ends of the molecular chain blocked with trimethylsiloxy groups and a viscosity of 40 mPa·s (25°C), 5.0 parts by mass of a nonionic surfactant (Pegnol T10/80, manufactured by Toho Chemical Industry Co., Ltd.) (F) as component, 59.9 parts by mass of purified water (G) as component, and acetic acid as a pH adjuster were mixed at 4000 rpm using an Ultra Turrax T50 Basic Shaft Generator G45M manufactured by IKA to prepare silicone emulsion (II).

The first and second liquids were mixed at a mixing ratio of 2.0, with a hydrogen-alkenyl ratio (NH/NA) of 2.0. Specifically, 100 parts of the first liquid and 6.4 parts of the second liquid were weighed out and mixed while stirring with a magnetic stirrer.

Example 2
First liquid: Same as silicone emulsion (I) of Example 1. Second liquid: Same as silicone emulsion (II) of Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 1.5. Specifically, the mixing ratio was 4.8 parts of the second liquid to 100 parts of the first liquid.

Example 3
First liquid: Same as silicone emulsion (I) of Example 1. Second liquid: Same as silicone emulsion (II) of Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.5. Specifically, the mixing ratio was 8.0 parts of the second liquid to 100 parts of the first liquid.

Example 4
First liquid: 0.7 parts of an alkenyl-containing polydimethylsiloxane (alkenyl group content 2.8 mmol/g) containing alkenyl groups at both ends and in the side chains and having a viscosity of 1000 mPa·s was used as component (E), and component (D) was blended so that the platinum content was [alkenyl groups in component (E) (mol)/platinum atoms (mol)] = 120, and the amount of purified water as component (G) was adjusted so that the components of first liquid were 100 parts by mass in total. Other than these points, the blending was the same as in Example 1 to prepare the first liquid.
Second liquid: Same as silicone emulsion (I) of Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Example 5
First liquid: the same as in Example 4. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 1.5.

Example 6
First liquid: the same as in Example 4. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.5.

Example 7
First liquid: The first liquid was prepared in the same manner as in Example 1, except that 0.09 part by mass of 3,5-dimethyl-1-hexyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (C).
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Example 8
First liquid: the same as in Example 7. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 1.5.

Example 9
First liquid: the same as in Example 7. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.5.

Example 10
First liquid: A first liquid was prepared in the same manner as in Example 1, except that 0.09 part by mass of 4-ethyl-1-octyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (C).
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Example 11
First liquid: the same as in Example 10. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 1.5.

Example 12
First liquid: the same as in Example 10. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.5.

(Example 13)
First liquid: 2.0 parts of an alkenyl-containing polydimethylsiloxane (alkenyl group content 1.7 mmol/g) containing alkenyl groups at both ends and in the side chains and having a viscosity of 600 mPa·s was used as component (E), and component (D) was blended so that the platinum content was [alkenyl groups (mol) in component (E)/platinum atoms (mol)] = 209, and the amount of purified water as (G) was adjusted so that the components of first liquid were 100 parts by mass in total. Other than these points, the blending was carried out in the same manner as in Example 1 to prepare the first liquid.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Example 14
First liquid: the same as in Example 13. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 1.5.

Example 15
First liquid: the same as in Example 13. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.5.

(Example 16)
First liquid: 0.8 parts of an alkenyl-containing polydimethylsiloxane (alkenyl group content 1.7 mmol/g) containing alkenyl groups at both ends and in the side chains and having a viscosity of 600 mPa·s was used as component (E), and component (D) was blended so that the platinum content was [alkenyl groups (mol) in component (E)/platinum atoms (mol)] = 84, and the amount of purified water as component (G) was adjusted so that the components of first liquid were a total of 100 parts by mass. Other than these points, the blending was the same as in Example 1 to prepare the first liquid.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

(Example 17)
First liquid: the same as in Example 16. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 1.5.

(Example 18)
First liquid: the same as in Example 16. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.5.

(Example 19)
First liquid: As the component (A), 25.0 parts by mass of alkenyl-containing polydimethylsiloxanes, each having a viscosity of 1,000 mPa·s and 20,000 mPa·s and each of which was end-blocked with a dimethylvinylsilyl group, were used. Except for this, the composition was blended in the same manner as in Example 1 to prepare the first liquid.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

(Example 20)
First liquid: the same as in Example 19. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 1.5.

Example 21
First liquid: the same as in Example 19. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.5.

Example 22
First liquid: 41.0 parts by mass of an alkenyl-containing polydimethylsiloxane with a viscosity of 1,000 mPa·s, both ends of which are blocked with dimethylvinylsilyl groups, was used as component (A), and 9.0 parts of an alkenyl-containing polydimethylsiloxane (alkenyl content 1.7 mmol/g) with a viscosity of 600 mPa·s, containing alkenyl groups at both ends and in the side chain, was used as component (E), and component (D) was blended so that the platinum content was [alkenyl groups (mol) in component (E)/platinum atoms (mol)] = 940, and the amount of purified water as component (G) was adjusted so that the components of the first liquid were a total of 100 parts by mass. Except for these points, the blending was performed in the same manner as in Example 1 to prepare the first liquid.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

(Example 23)
First liquid: the same as in Example 22. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 1.5.

Example 24
First liquid: the same as in Example 22. Second liquid: the same as in Example 1. The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.5.

Comparative Example 1
First liquid: Component (E) was not blended, and the amount of purified water as component (G) was adjusted so that the total amount of components in first liquid was 100 parts by mass. Other than these points, the blending was the same as in Example 1.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Comparative Example 2
First liquid: 0.2 parts of an alkenyl-containing polydimethylsiloxane (alkenyl group content 2.8 mmol/g) containing alkenyl groups at both ends and in the side chains and having a viscosity of 1000 mPa·s was used as component (E), and component (D) was blended so that the platinum content was [alkenyl groups in component (E) (mol)/platinum atoms (mol)] = 20, and the amount of purified water as component (G) was adjusted so that the components of first liquid were 100 parts by mass in total. Other than these points, the blending was the same as in Example 1 to prepare the first liquid.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Comparative Example 3
First liquid: Component (C) was not blended, and the amount of purified water as component (G) was adjusted so that the total components of the first liquid were 100 parts by mass. Other than these points, the blending was carried out in the same manner as in Example 1 to prepare the first liquid.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Comparative Example 4
First liquid: Component (C) was not blended, and the amount of purified water as component (G) was adjusted so that the total components of the first liquid were 100 parts by mass. Other than these points, the blending was carried out in the same manner as in Example 1 to prepare the first liquid.
Second liquid: 0.09 parts by mass of 1-ethynyl-1-cyclohexanol (manufactured by Nissin Chemical Industry Co., Ltd.) was used as component (C), and the amount of purified water as component (G) was adjusted so that the total components of the second liquid was 100 parts by mass. Other than these points, the blending was carried out in the same manner as in Example 1 to prepare the second liquid.
The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Comparative Example 5
First liquid: Same as Comparative Example 4
Second liquid: Same as Comparative Example 4. The first and second liquids were mixed so that the hydrogen-alkenyl ratio (NH/NA) was 12.8. In other words, the ratio of the platinum catalyst (component (D)) and the inhibitor (component (C)) in the two-liquid mixture was the same as in Example 1.

Comparative Example 6
First liquid: 40.0 parts by mass of alkenyl-containing polydimethylsiloxane with a viscosity of 1,000 mPa·s, both ends of which are blocked with dimethylvinylsilyl groups, was used as component (A), 10.0 parts of alkenyl-containing polydimethylsiloxane (alkenyl content 0.24 mmol/g) with a viscosity of 20,000 mPa·s, containing alkenyl groups at both ends and in the side chain, was used as component (E), and component (D) was blended so that the platinum content was [alkenyl groups (mol) in component (E)/platinum atoms (mol)] = 147, and the amount of purified water as component (G) was adjusted so that the total components of the first liquid was 100 parts by mass. Except for these points, the blending was the same as in Example 1 to prepare the first liquid.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Comparative Example 7
First liquid: Instead of component (E), for comparison, 0.2 parts of 1,3-divinyltetramethyldisiloxane (alkenyl group content 10.7 mmol/g) containing alkenyl groups at both ends and having a viscosity of up to 1.0 mPa·s was used, and component (D) was blended so that the platinum content was [alkenyl groups (mol) in the 1,3-divinyltetramethyldisiloxane component/platinum atoms (mol)] = 131, and the amount of purified water as component (G) was adjusted so that the components of first liquid totaled 100 parts by mass. Apart from these points, the blending was the same as in Example 1 to prepare the first liquid.
Second liquid: The first liquid and the second liquid were mixed in the same manner as in Example 1 so that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Comparative Example 8
First liquid: 0.09 parts by mass of 3,5-dimethyl-1-hexyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the (C) component, the (E) component was not blended, and the amount of purified water as the (G) component was adjusted so that the total components of the first liquid were 100 parts by mass. The first liquid was prepared in the same manner as in Example 1, except for these points.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

Comparative Example 9
First liquid: 0.09 parts by mass of 4-ethyl-1-octyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the (C) component, the (E) component was not blended, and the amount of purified water as the (G) component was adjusted so that the total components of the first liquid were 100 parts by mass. Except for these points, the blending was carried out in the same manner as in Example 1 to prepare the first liquid.
Second liquid: Same as in Example 1 The first and second liquids were mixed at a mixing ratio such that the hydrogen-alkenyl ratio (NH/NA) was 2.0.

(Evaluation method)
<Determination of Curing Speed>
The two-liquid addition curable composition prepared and mixed by the above method was applied to one side of Ester G2C (50 μm thick) manufactured by Toyobo Co., Ltd., and dried by heating in an oven at 150° C. The time required for the coated surface to completely cure was measured, and this curing time (curing speed) was evaluated according to the following criteria. A grade of B or higher was deemed acceptable.
A: Less than 30 seconds
B: 30 seconds or more but less than 60 seconds
C: 60 seconds or more but less than 120 seconds
D: 120 seconds or more
E: Not measurable (uncured, etc.)

<Criteria for determining completion of curing>
In the above-mentioned evaluation of the curing rate, the completion of curing was evaluated as follows.
After curing, the surface of the peelable coating was rubbed strongly with a finger five times. If the coating surface became cloudy and white (a condition called smearing), it was judged to have not cured sufficiently. If no change was observed on the rubbed coating surface, it was judged to have no problems with curing and to have completed curing.

<Method of producing release film>
The two-liquid addition curable composition prepared and mixed by the above method was applied to one side of Ester G2C (thickness: 50 μm) manufactured by Toyobo Co., Ltd. using a Mayer bar coater No. 3. The composition was heated and cured in an oven at 150° C. for 2 minutes to prepare a release film sample.

<Method for measuring peel strength>
The release film prepared by the above method was kept at room temperature for 30 minutes or more, after which TESA7475 (a tape for checking silicone coating performance, manufactured by Tesa Tape Co., Ltd.) was laminated to the coated surface, pressed with a roller, and a weight of 20 g/ ^cm2 was placed on it, and this state was kept at 40°C for 20 hours. After that, the peel force was measured when peeling the tape from the film at a peel angle of 180° and a peel speed of 0.3 m/min (see FINAT Test Method No. 10 (FINAT Technical Handbook ^9th edition, 2014)).

<Residual adhesion rate measurement method>
A polyester adhesive tape Nitto No. 31B (manufactured by Nitto Denko Corporation) was attached to the coated surface of the release film prepared as described above, pressed with a roller, and aged at 40°C for 20 hours with a weight of 20 g/ ^cm2 . The adhesive tape peeled off from the release film after aging was pressed with a roller onto a stainless steel plate, and then the peeling force of the adhesive tape was measured at a peeling angle of 180° and a peeling speed of 0.3 m/min. The value of the peeling force at that time was taken as the peeling force against the stainless steel plate after being attached to the release film. In addition, a polyester adhesive tape Nitto No. 31B (manufactured by Nitto Denko Corporation) was pressed with a roller onto a stainless steel plate, and then the peeling force of the adhesive tape was measured at a peeling angle of 180° and a peeling speed of 0.3 m/min. The value of the peeling force was taken as the peeling force against the stainless steel plate of the blank (not attached to the release film of the present invention). The value calculated by the following formula was taken as the residual adhesion rate (%).
Residual adhesion rate (%) = (peel force from stainless steel plate after bonding to release film) / (peel force from blank stainless steel plate) x 100

<Visual evaluation of composition appearance (discoloration)>
In two-part addition curable compositions, appearance abnormalities often occur in the first part, which contains a platinum catalyst. If appearance abnormalities occur in the first part, the cured product obtained by curing the two-part addition curable composition using this will also have appearance abnormalities. Therefore, the degree of appearance (discoloration) of the first part was evaluated.
For the first liquid, components (A), (C), (D), and (E) were mixed and left to stand for one day, and the color of the composition was visually inspected for any change and evaluated according to the following criteria. A score of B or higher was considered to be acceptable.
A: Transparent (no change)
B: Light yellow
C: Dark yellow to brown
D: Black

<Visual evaluation of the cured product>
For the two-component addition curable composition, a release film (a cured film, which is a cured product of the two-component addition curable composition of the present invention) was prepared according to the above-mentioned method for preparing a release film, and the appearance was visually confirmed. If the appearance of the cured film was colorless and transparent, it was judged to be normal, and if the cured film was colored and changed color to yellow, brown, black, or the like, it was judged to be abnormal. If the cured film did not cure, the cured product was not evaluated, and it was rated as unsuccessful (indicated as "-" in the table).

<Pot life evaluation>
The workable time (pot life) after mixing the first and second liquids was evaluated. The first and second liquids of the two-part addition curable composition were mixed at room temperature, placed in a plastic container, covered, and visually observed for the presence or absence of solid matter on the liquid surface. The time until solid matter (usually gel-like) was generated in the composition was defined as the workable time, and evaluation was performed according to the following criteria. B or higher was considered to be acceptable.
A: More than one day
B: Half a day or more
C: More than 1 hour but less than half a day
D: Less than 1 hour

(result)
As is clear from the results shown in the table, the results of Examples 1 to 24 were excellent, being rated B or higher in all of the curability evaluation, appearance evaluation, and pot life evaluation.
Furthermore, the composition of the present invention can maintain the curing speed at a desired level even when the mixing ratio of the first and second liquids is changed to change the ratio of the alkenylorganopolysiloxane to the organohydrogenpolysiloxane, and can be used without affecting workability such as pot life. Furthermore, no abnormalities in appearance were observed, and it was confirmed that it is possible to change the curing characteristics to the desired level.

When the hydrogen-alkenyl ratio (NH/NA) was mixed within the range of 1.3≦(NH/NA)≦4.0, the residual adhesion rate was 85% or higher in all cases, confirming that the release agent produced a good cured film with little migration to the material being removed.

As seen in Comparative Examples 1, 7, 8, and 9, when component (E) was not added, abnormal appearance was observed in all cases. Component (E) is considered to have the function of stabilizing the platinum complex of component (D) and reducing the strong interaction with the inhibitor of component (C), and the results support that component (E) is an essential component for the composition of the present invention.

Furthermore, even when an inhibitor having a different structure was used as component (C) (Examples 4 to 6), it was confirmed that component (E) was able to coordinate well with the platinum catalyst of component (D) and exert the effect of suppressing appearance abnormalities.
On the other hand, when an (E) component with an alkenyl group content outside the specified range (Comparative Example 6) or viscosity outside the specified range (Comparative Example 7) was used, or when the blending amount of the (E) component did not satisfy the specified range (Comparative Example 2), abnormal appearance was also observed.

In Comparative Example 3, where no inhibitor of component (C) was added, and Comparative Example 4, where an inhibitor of component (C) was added to the second liquid, although no abnormalities in appearance were observed, the pot life was significantly reduced. Even when an inhibitor of component (C) was added to the second liquid, it was possible to adjust the amount of inhibitor of component (C) relative to the platinum catalyst of component (D) by adjusting the amount of the second liquid added, as in Comparative Example 5, but it was not possible to freely change the mixing ratio of the first liquid and the second liquid. Furthermore, the addition of an excessive amount of the second liquid resulted in a significant change in the peeling properties (Comparative Examples 4 and 5).

The two-part addition curable composition kit of the present invention functions favorably as a release material that can maintain a constant curing speed and pot life even when the user changes the mixing ratio of the first and second parts. By forming a cured film obtained by curing the two-part addition curable composition on the surface of a thin substrate such as paper or plastic, it is possible to provide release paper, release film, etc., with good adhesion to these substrates.

Claims (6)

A two-part addition curable composition kit comprising a first liquid and a second liquid,
The first liquid is
Component (A): an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals per molecule and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less;
(C) component: an inhibitor;
(D) component: a platinum catalyst;
Component (E): an organopolysiloxane having at least one alkenyl group bonded to a silicon atom in a side chain of the molecular chain, with an alkenyl group content per molecule of 1.0 mmol/g or more and a viscosity at 25°C of 100 mPa·s or more and 100,000 mPa·s or less;
Including,
The first liquid does not contain organohydrogenpolysiloxane,
the amount of the component (E) blended in the first liquid is an amount such that the molar ratio of alkenyl groups in the component (E) to platinum atoms [alkenyl groups in the component (E)/platinum] is 50 or more and 1,000 or less;
The second liquid is
Component (B): An organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in each molecule,
the second liquid does not contain the component (A), the component (C), the component (D), or the component (E);
The first liquid and the second liquid each further include
(F) component: an emulsifier,
(G) Ingredient: Water,
Including,
By mixing the first liquid and the second liquid, an emulsion-type addition curable composition can be obtained.
A two-part addition curable composition kit comprising: The component (C) is an alkynol compound,
The component (D) is a platinum-vinylsiloxane complex.
2. The two-part addition curable composition kit according to claim 1 . The first liquid further comprises a preservative;
The second liquid further contains a pH adjuster.
2. The two-part addition curable composition kit according to claim 1 . A method for producing a two-part addition curable composition kit, comprising:
a base compounding step of compounding component (A) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals per molecule and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less;
a catalyst protection step of mixing an organopolysiloxane as component (E) having at least one alkenyl group bonded to a silicon atom in a molecular side chain, an alkenyl group content per molecule of 1.0 mmol/g or more, and a viscosity at 25°C of 100 mPa·s or more and 100,000 mPa·s or less with a platinum catalyst as component (D) to obtain a protected catalyst;
a step of preparing a protected catalyst composition by mixing the protected catalyst with an inhibitor as component (C) to obtain a protected catalyst composition;
A first liquid manufacturing process including the steps of:
(B) a second liquid production step of producing a second liquid containing an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in one molecule as a component;
A method for producing a two-part addition curable composition kit, comprising: A method for producing an emulsion-type two-part addition curable composition kit, comprising the steps of:
a base compounding step of compounding component (A) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms only at the molecular chain terminals per molecule and having a viscosity at 25°C of 10 mPa·s or more and 1,000,000 mPa·s or less;
a catalyst protection step of mixing an organopolysiloxane as component (E) having at least one alkenyl group bonded to a silicon atom in a side chain of the molecular chain, an alkenyl group content per molecule of 1.0 mmol/g or more, and a viscosity at 25°C of 100 mPa·s or more and 100,000 mPa·s or less, with a platinum catalyst as component (D) to obtain a protected catalyst;
a step of preparing a protected catalyst composition by mixing the protected catalyst with an inhibitor as component (C) to obtain a protected catalyst composition;
a first liquid emulsification step of adding an emulsifier as a component (F) and water as a component (G) to a composition containing the protected catalyst composition and the component (A) to obtain a first emulsion;
a second emulsification step of obtaining a second emulsion containing an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in one molecule as the component (B), the component (F), and the component (G);
A method for producing an emulsion-type two-part addition curable composition kit, comprising: A substrate;
A cured coating formed on a substrate by curing the addition curable composition according to any one of claims 1 to 3 ;
A peelable material comprising: