JP3907230B2 - PARTICLE, PARTICLE-CONTAINING DISPERSION AND PROCESS FOR PRODUCING THEM - Google Patents

Description

【０１７２】
【表−２】

【０１７３】
【発明の効果】
表−１及び２に示した実施例及び比較例の評価結果の比較対照により明らかなように、エマルジョン組成物から得られる被膜（塗膜、フィルム等）の諸特性に関し、本発明に係るエマルジョン組成物の場合は、従来技術によるエマルジョン組成物による場合と比較して、優れた耐水性、耐溶剤性、密着性及び耐ブロッキング性を有している。
本発明に係る水系分散性被覆組成物は、少なくとも、次の(1) 〜(4) の特徴を有する。
【０１７４】
(1) シリカを有機高分子との共有結合によるのではなく、有機高分子の網目構造により物理化学的及び又は二次的結合（水素結合、疎水結合、ファンデルワールス結合等）により粒子中に保持しているので、有機高分子中にゲル化の原因となるシリカとの反応性を有する官能基が存在せず、そのため、粒子又は粒子含有組成物の貯蔵安定性に優れる。
(2) 前記組成物は、貯蔵安定性に優れた一液型（使用直前に混合操作が不要な一成分系）であるので、二液型（例えば、使用直前に樹脂成分と硬化剤成分を混合する二成分系）と比較して、ポットライフが長く、操作性がよい。
(3) 前記組成物に含まれるコア／シェル粒子は、塗膜形成時又はフィルム形成時に、三次元架橋構造を構築するので、ＭＦＴ（最低被膜形成温度）以上で被膜形成した際に、得られる被膜に、優れた耐久性（耐溶剤性、耐熱性、下地との接着性、耐水性）、優れた物理特性（弾性、伸び特性、強靱性）、優れた外観特性（平滑性、鮮映性等）を発揮する。
(4) 前記組成物に含まれるコア／シェル粒子は、コア内にシリカが存在し、シリカを共有結合によることなく有機高分子の網目構造により物理化学的及び又は二次的結合（水素結合、疎水結合、ファンデルワールス結合等）により粒子中に保持しているので、優れた耐ブロッキング性を有する。
【０１７５】
したがって、本発明に係るエマルジョン組成物は、塗料、被覆剤、オーペイク剤、接着剤、印刷インキ、紙加工、感熱紙・感圧紙加工、繊維加工、織物用増粘剤、顔料分散剤、化粧用配合物、セメント混和剤などの広い分野にわたって好適に使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention has a core / shell structure, an organic polymer that is not covalently bonded to the core and silica and / or colloidal silica, and an organic polymer that is disposed in the shell. By forming a three-dimensional crosslinked network structure and / or IPN (inter-penetrating network) structure between the shell organic polymers, the silica and / or colloidal silica in the core can be held in the particles physicochemically without being covalently bonded. When the film is formed at a temperature higher than the Tg (glass transition point) of the particles or the MFT (minimum film forming temperature) of the composition containing the particles, the silica or colloidal silica is physicochemically held in the film without being covalently bonded. , Grains with functions that can exhibit excellent water resistance, solvent resistance, adhesion, blocking resistance, durability, physical properties, appearance properties, etc. Regarding the child.
[0002]
Furthermore, the present invention relates to a core / shell particle having a core in which a polymer having an epoxy group and colloidal silica are present, and a shell in which a polymer having a functional group reactive with the epoxy group is present.
Furthermore, the present invention relates to a core / shell particle having a core having a functional group reactive with an epoxy group and a core in which colloidal silica is present, and a shell having a polymer having an epoxy group.
Furthermore, the present invention relates to an aqueous dispersible composition having the characteristics of an emulsion, latex or suspension containing the particles as a dispersed phase and water as a continuous phase.
Furthermore, this invention relates to the water-based dispersible coating composition which contains the said water-based dispersible composition as a main component.
Furthermore, this invention relates to the manufacturing method of the said particle | grain.
[0003]
Concept of the words “core”, “shell” and “core / shell”
The terms “core”, “shell” and “core / shell” as used in the claims and specification of this application fully encompass the concepts these terms generally have in polymer chemistry, but not necessarily. It is not equivalent. For example, with respect to the “core / shell” particles according to the present invention, a mode in which the “core” is at least partially encased in the “shell”, microvoids (microvoids, voids, cavities in the core or particles). The same as in the following description), one or more microvoids in the core or particles, and one or more passages that connect the spaces outside the particles. Such an aspect is also included. Thus, the terms “core”, “shell”, and “core / shell” used in the claims and specification of this application are not necessarily equivalent to the concepts that these terms generally have in polymer chemistry. Although not, it will be used for convenience in making frequent references to the essential “embodiments” of the heteropolymer system according to the present invention.
[0004]
In polymer chemistry, the term “core” is generally equivalent to the terms “core, center, nucleus”, “core, center”, and “seed”. As used, the term “shell” is used equivalently to the terms “shell, skin, husk”, “sheath”, and “robe”.
Accordingly, as used in the claims and specification of this application, the term “core” refers to the terms “core, center, nucleus”, “core, center”, and “seed”. Can be used in the same manner.
Similarly, the term “shell” can be used equivalently to the terms “shell, skin, husk”, “sheath”, and “robe”.
[0005]
The concept of the word “particle”
The concept of the term “particle” as used in the claims and specification of this application completely encompasses, but is not necessarily equivalent to, the concept that these terms generally have in polymer chemistry. Regarding the aspect of the scanning electron microscopic form of the “particle” used in the claims and specification of the present application, for example, an aspect having many protrusions in the form of raspberry or gold rice sugar (compete, Portuguese confeito) , Erythrocyte-like flat aspect, rugby ball-like spheroid-like aspect, E. coli-like spindle-like aspect, hollow particle-like aspect having one or more voids inside, like bell Examples include an embodiment in which non-hollow particles are further included in the hollow particles, an embodiment in which one or more hollow particles are further provided inside the hollow particles, such as matryoshka, a Russian folkcraft. The concept of the term “particle” used in the claims and specification of the present application includes, for example, a polymer emulsion, a latex, and a microsphere constituting a polymer suspension. Thus, the term “particle” as used in the claims and specification of the present application is not necessarily equivalent to the concept that these terms generally have in polymer chemistry. It will be used for convenience in making frequent references to the essential “embodiments” of the heteropolymer system according to the invention.
[0006]
Concept of “continuous emulsion polymerization or suspension polymerization”, “multi-stage continuous polymerization” or “continuous polymerization”
The concept of “continuous emulsion polymerization or suspension polymerization”, “multistage continuous polymerization” or “continuous polymerization” used in the claims and specification of the present application is an aqueous continuous phase (aqueous medium). The one or more polymers on the seed polymer are polymerized by applying the pre-formed particles, i.e. seed polymer particles, with the monomer in one or more subsequent steps and polymerizing. It includes emulsion polymerization or suspension polymerization techniques that deposit one or more polymer layers and increase the particle diameter by depositing. Here, the term “monomer” includes one or more kinds of monomers, and the term “polymer” includes homopolymers and copolymers.
The arrangement mode of the copolymer (copolymer) may be any of random copolymer, alternating copolymer, block copolymer, graft copolymer, and the like.
[0007]
Features of the water-based dispersible coating composition according to the present invention
The water-based dispersible coating composition according to the present invention has at least the following characteristics (1) to (4).
(1) Silica is not covalently bonded to organic polymer, but physicochemical and / or secondary bond (hydrogen bond, hydrophobic bond, van der Waals bond, etc.) in the particle by the network structure of organic polymer. Since it is held, there is no functional group having reactivity with silica that causes gelation in the organic polymer, and therefore, the storage stability of the particles or the particle-containing composition is excellent.
(2) Since the composition is a one-pack type (one-component system that does not require a mixing operation just before use) having excellent storage stability, a two-pack type (for example, a resin component and a curing agent component are used just before use). Compared with the two-component system to be mixed), the pot life is long and the operability is good.
(3) Since the core / shell particles contained in the composition form a three-dimensional cross-linking structure at the time of coating film formation or film formation, the core / shell particles are obtained when the film is formed at MFT (minimum film forming temperature) or higher. Excellent durability (solvent resistance, heat resistance, adhesion to ground, water resistance), excellent physical properties (elasticity, elongation properties, toughness), excellent appearance properties (smoothness, sharpness) Etc.).
(4) The core / shell particles contained in the composition have silica in the core, and physicochemical and / or secondary bonds (hydrogen bonds, It has excellent blocking resistance because it is retained in the particles by hydrophobic bonds, van der Waals bonds, etc.
[0008]
Specific examples of uses of the water-based dispersible coating composition according to the present invention
The water-based dispersible coating composition is a paint, a coating agent, an opaque agent, an adhesive, printing ink, paper processing, thermal paper / pressure-sensitive paper processing, fiber processing, textile thickener, pigment dispersant, cosmetic compound. And can be suitably used in a wide range of fields such as cement admixtures.
[0009]
blocking
The term “blocking” used in the claims and the specification of the present application is, for example, the new version of the Dictionary of Polymers (edited by the Society of Polymer Science, Asakura Shoten, Tokyo, 1988). ”Means“ blocking ”. Specifically, for example, when a painted product is stacked or a heavy object is left on the painted surface, the contact surface is It means a sticking phenomenon that is bonded and cannot be easily peeled off.
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
[0010]
Examples of common causes of coating blocking include the following (1) to (5).
(1) Since the glass transition point (Tg) of the coating film forming element is low, the coating film softens in a high temperature environment and exhibits adhesiveness.
(2) Since the coating film is not sufficiently cured, it exhibits adhesiveness.
(3) The plasticizer in the coating film migrates and develops adhesiveness.
(4) The solvent remains in the coating film and develops adhesiveness.
(5) In a humid environment, the coating film swells with moisture and develops adhesiveness.
[0011]
Blocking resistance
The term “blocking resistance” generally means a property that pressure-bonding property does not appear in a coating film (coating film, film, etc.) formed by particles applied to a base (substrate, base material) by some means.
The term “blocking resistance” used in the claims and specification of the present application includes the above-mentioned general concept of “blocking resistance” in addition to the generally used concept of “blocking resistance”. The concept of “contamination resistance” is also included.
[0012]
Stain resistance
The term “contamination resistance” generally means the property that foreign matter adhesion does not appear in a film (coating film, film, etc.) formed by particles applied to a base (substrate, base material) by some means.
[0013]
Unimodal Continuously Polymerized Heteropolymer
In multi-stage continuous polymerization, in the next stage following from one stage, if no additional surfactant is added at all, virtually no micelles are formed in the reaction system, so that it exists in the reaction system at that stage. All the monomers are incorporated on the particles obtained from the reaction system of the immediately preceding stage and are physically and / or chemically closely bonded.
When such a reaction mode is adopted consistently in the process of particle production, in principle, particles having only one kind of core / shell structure or polymer deposition structure can be obtained regardless of actual results. It should be.
Such particles are referred to as “unimodal” continuously polymerized heteropolymers. The single aspect continuous polymerization heteropolymer is described in more detail, for example, in Japanese Patent Publication No. 3-9124 (Kowalski et al.), Column 10, line 31 to column 11, line 8.
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
[0014]
Polymodal Continuously Polymerized Heteropolymer
On the other hand, if a surfactant is added in an amount that can form micelles in the next step, that is, a CMC (critical micelle formation concentration) or more, it is present in the reaction system at that step. For some monomers, a portion of the monomer is incorporated onto the particles obtained from the reaction system of the immediately preceding stage and is physically and / or chemically closely bonded, while the remaining portion of the monomer is It is not incorporated on the particles obtained from the stage reaction system, but is incorporated into additional micelles to produce additional particles.
[0015]
When such a reaction mode is employed in the particle production process, in principle, it should be possible to obtain particles having a wide variety of core / shell structures or polymer deposition structures, regardless of actual results.
Such particles are referred to as “polymodal” —for example, “binary”, “ternary” or “multimodal” —continuously polymerized heteropolymers. The polymorphic continuous polymerization heteropolymer is described in more detail, for example, in JP-B-3-9124 (Kowalski et al.), Column 10, line 31 to column 11, line 8.
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
In order to realize the production of particles having the intended “single aspect” or “multiple aspect”, the surfactant type, concentration, addition mode, timing and period of addition, etc. What is necessary is just to set suitably a relative ratio etc. with a monomer.
[0016]
Multiple aspects of particles according to the present invention
The particles according to the present invention may be monomorphic or multimodal. In the case of polymorphism, binary aspect is generally preferred. In the case of polymorphism, it is generally preferred that the main aspect comprises about 60% to about 90%, more preferably about 75% to about 85%.
[0017]
Seed polymer
The concept of the term “seed polymer” as used in the specification of this application is pre-generated polymer particles, excluding the first stage polymer particles in polymerization or the final stage of continuous polymerization. It can be the product polymer particles at any stage. Thus, a polymer particle intended to be subsequently provided with a shell by one or more successive steps is itself a seed polymer for that step in the next step of depositing the shell-forming polymer on the seed polymer particle. Called. Thus, the seed polymer or core can be produced in a single stage or continuous polymerization process.
[0018]
Evaluation of glass transition point (Tg) of heteropolymer
The glass transition point (Tg) of a polymer having a specific monomer composition can be determined by calculation using the Fox equation. Here, the Fox formula is for calculating the Tg of the copolymer based on the Tg of the homopolymer of the monomer for each monomer forming the copolymer, The details thereof are described in Bulletin of the American Physical Society, Series 2 (Volume of the American Physical Society, Series 2) Vol. 1, No. 3, p. 123 (1956).
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
[0019]
The Tg of various ethylenically unsaturated monomers, which are the basis for evaluating the Tg of copolymers according to the Fox formula, is, for example, Shin Polymer Library, Volume 7, Introduction to Synthetic Resins for Paints (Kyozo Kitaoka) , Kobunshi Shuppankai, Kyoto, 1974) The values described in Table 10-2 (main raw material monomers for acrylic resins for paints) on pages 168 to 169 can be employed.
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
[0020]
[Prior art]
R & D trends in paint technology from the viewpoint of ecology, etc., and expectations for emulsion-type paints
In recent years, in the technical field of paints, expectations for emulsion-type paints have been increasing in place of solvent-type paints from the viewpoint of local or global environmental protection and occupational health and safety environment improvement. As the expectation for higher functionality and diversification of emulsion-type paints grows due to historical or social demands, advanced paint film performance (for example, durability) comparable to that of solvent-type paints is applied to emulsion-type paints. , Blocking resistance, etc.) have been required.
[0021]
Problems of emulsion paints
In recent years, although emulsion-type paints have begun to be used for inorganic bases, etc., “water” is caused by coating film defects due to poor film formation of emulsion particles and large amounts of additives (hydrophilic emulsifiers, thickeners, etc.). The problem that the durability of the coating film is far inferior to that of the solvent-based paint due to the “bake” phenomenon, etc. has not been solved yet.
That is, despite the fact that the coating film performance required for emulsion-type paints has become severe, it cannot necessarily be said that emulsion-type paints that satisfy such requirements have been put on the market.
In particular, when an emulsion-type paint is applied to form a coating film, it is extremely difficult to simultaneously exhibit excellent durability and excellent blocking resistance. Consisting of excellent durability and excellent anti-blocking properties for coating films is a long-standing and inevitable problem in the technical field of emulsion-type paints. Until now, a huge amount of research resources have been invested.
[0022]
Emulsion-type paint film formation mechanism
The mechanism of film formation (film formation, film formation, film formation) of emulsion-type paint is uniform only after the particles existing in the emulsion come into contact with each other on the base and develop thermal fusion between the particles. It is believed that a good coating is formed.
In the theory of the film formation mechanism of emulsion-type paints, MFT is important in addition to the importance of Tg.
[0023]
MFT (Minimum film formation temperature)
MFT is the minimum film forming temperature of the particles contained in the composition when the coating composition such as paint is dried. MFT can be easily evaluated by a modified method described in Resin Review, Vol. 16, No. 2 (1966).
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
[0024]
The principle of this evaluation method is that a composition in which particles are dispersed is thinly applied on a temperature gradient bar, and the temperature at which a thin film is formed is evaluated very simply and quickly. .
The temperature at which the thin film starts to be formed is determined by, for example, the boundary between the temperature zone where the non-coated opaque particle dispersion composition is continuously present and the temperature zone where the coated transparent film is continuously present. It can be confirmed optically.
In addition, the temperature at which the thin film starts to be formed is a temperature zone where a non-coated particle dispersion composition that can be scraped off continuously using a spatula and a film that cannot be scraped off are continuously formed. It is also possible to physically confirm the boundaries of the existing temperature zones.
MFT is not only affected by the Tg of the polymer that makes up the particles, but also plastics with additives (film-forming aids, plasticizers, hydrophilic emulsifiers, thickeners, binders, etc.), water, organic solvents, etc. It can be influenced by effects.
[0025]
Problems related to blocking resistance of emulsion paints.
Therefore, in the case of emulsion-type paints, it is necessary to design the polymer to have a relatively low Tg value compared to the case of solvent-type paints, and therefore the anti-blocking property of the coating film is also inferior. There was a problem.
[0026]
Traditional approaches to the problems of emulsion-type paints
Two major problems with such emulsion-type paints, that is, the contradictory “twin defects” that are difficult to solve simultaneously, (1) problems related to the durability of the paint film, and (2 ) In order to solve the problems related to blocking resistance, for example, many researches and developments based on the following approaches (technical ideas) (1) to (8) have been vigorously promoted.
[0027]
(1) Approach for adding film-forming auxiliary
This is an approach for forming a film at room temperature by adding a large amount of a film-forming auxiliary to an emulsion containing polymer particles having a relatively high Tg value.
In the case of such an approach, the selection of a film-forming auxiliary is a big point.
When a film-forming auxiliary having a relatively high volatility is used, the film-forming becomes insufficient and the coating film is likely to crack.
On the other hand, when a film-forming auxiliary with low volatility is used, the coating film continues to be “sticky” even after several days to several weeks after application, and this phenomenon causes a problem in blocking resistance. Arise.
Therefore, in the case of the approach based on the addition of a film-forming auxiliary agent, there remains a problem of searching for a better chemical substance that can solve the “twin defect”.
[0028]
(2) Multi-layer polymerization approach
The approach by the multilayer polymerization method is to arrange a polymer composition having a high Tg value in the inner layer and to prepare a multilayer polymer particle having a polymer composition having a low Tg value in the outer layer. Based on the technical idea of exhibiting interparticle adhesion and film-forming properties with a low Tg value polymer composition, and simultaneously exhibiting anti-blocking properties with a high Tg value polymer composition after coating film formation. ing.
In such an approach, the larger the difference in Tg value between the inner layer and the outer layer, the more markedly the blocking resistance is improved. There was a problem of accompanying deterioration due to poor compatibility.
On the other hand, the smaller the difference in the Tg value between the inner layer and the outer layer, the better the compatibility between the inner and outer layers of the polymer, so the durability is improved. Has a problem that it is accompanied by deterioration due to a relative decrease in Tg of the outer layer polymer composition.
Therefore, many problems to be solved still remain in the case of the approach by the multilayer polymerization method.
[0029]
(3) Emulsion blend approach
Unlike the multilayer polymerization method described above, the emulsion-blend approach requires a coating composition mainly composed of a high Tg polymer particle-containing emulsion and a blend or cocktail with a low Tg polymer particle-containing emulsion under appropriate conditions. When the coating film is formed, the inter-particle fusion property and the film-forming property are exhibited by the low Tg value polymer particles, and at the same time, the blocking property is exhibited by the high Tg value polymer particles after the coating film is formed. This is based on the technical idea to be made.
[0030]
In the case of such an approach, similar to the approach by the multilayer polymerization method, regarding the polymer particle having a low Tg value and the polymer particle having a high Tg value, the larger the difference between the Tg values of the two, Although the blocking property is remarkably improved, in contrast, the durability is accompanied by a deterioration due to a poor compatibility between the two.
On the other hand, the smaller the difference between the Tg values of the two, the better the compatibility between the two, so that the durability is improved, but in contrast, a polymer having a high Tg value with respect to blocking resistance. There was a problem of accompanying deterioration due to the relative decrease in Tg of the particles.
Therefore, there are still many problems to be solved by the emulsion blend approach.
[0031]
(4) Approach by blending “inorganic compound / organic polymer particle-containing emulsion”
The approaches (1) to (3) are all based on the technical idea of using particles containing only organic polymers as constituent elements.
From the viewpoint that there is a limit to trying to solve the problem based on such a technical idea, for example, an inorganic compound such as water glass, colloidal silica, imogolite and the like is blended with an organic polymer. There are approaches that attempt to improve durability and blocking resistance simultaneously.
[0032]
In this approach, a coating composition mainly composed of a blend composition with a polymer emulsion containing inorganic compounds and organic polymer particles is prepared under appropriate conditions. It is based on the technical idea that the interparticle adhesion and film-forming property are exhibited by the particles, and at the same time, after forming the coating film, the blocking resistance is exhibited by the inorganic compound.
In the case of such an approach, the anti-blocking property is excellent because the hardness of the obtained coating film is high.
However, regarding durability (for example, water resistance, alkali resistance, acid rain resistance, etc.), there is a problem because the bonding property between the inorganic compound and the organic polymer is low.
[0033]
(5) Approach by blend of “inorganic compound / organic polymer particle-containing emulsion / alkoxysilane group-containing low molecular weight compound”
In order to solve the problems related to the low bonding property between the inorganic compound and the organic polymer in the above-mentioned approach by the blend of “inorganic compound / organic polymer particle-containing emulsion”, the effect of strengthening the binding property between the two is effective. There is an approach of adding alkoxysilanes having them.
However, the blend composition prepared on the basis of such a technical idea has a problem that the storage stability of the composition itself is low and it cannot withstand medium- and long-term storage and storage.
[0034]
(6) Approach by blend of “inorganic compound / emulsion containing alkoxysilane group-containing organic polymer particles”
In order to solve the problems related to the storage stability of the blend composition in the above-mentioned blend-based approach of “inorganic compound / emulsion containing organic polymer particles / low molecular compound having alkoxysilane group”, alkoxy which is a factor of instability There is an approach in which an organic polymer particle-containing emulsion having an alkoxysilane group is used as the organic polymer particle-containing emulsion without adding a low molecular compound having a silane group.
For example, the technique disclosed in Japanese Patent Application Laid-Open No. 59-71316 (Japanese Patent Publication No. 4-48832, Yoshiaki Hasegawa and Fumio Yoshino) is based on such an approach. In JP-A-59-71316, (A): acrylic copolymer, etc., (B); silane monomer, (C); colloidal silica is emulsion-copolymerized in an aqueous medium at a specific ratio. A technique relating to a water-dispersible coating composition capable of expressing a coating film containing the resulting resin dispersion as a main component and having excellent durability and blocking resistance is disclosed. Here, the monomer (A) is selected from the group consisting of α, β-monoethylenically unsaturated carboxylic acid alkyl esters (eg, methyl acrylate, methyl methacrylate, etc.) and alkenylbenzenes (eg, styrene, etc.). It is at least one monomer, and the monomer (B) is a monomer having a polymerizable unsaturated double bond and an alkoxysilane group in the molecule (for example, divinyldimethoxysilane).
[0035]
Such a composition is excellent in the storage stability of the composition itself. Moreover, since the obtained coating film is formed by combining acrylic emulsion and colloidal silica, it has excellent durability (for example, water resistance, alkali resistance, acid rain resistance, etc.) and blocking resistance.
However, since the organic polymer component of the obtained coating film does not have a three-dimensional crosslinked structure, durability (for example, solvent resistance, heat resistance, mechanical properties, adhesiveness, etc.) is low and there is a problem.
In addition, when synthesizing an organic polymer having an alkoxysilane group in the molecule, a monomer having an alkoxysilane group is used. Therefore, in the synthesis process, the alkoxysilane group is hydrolyzed and easily gelled. is there.
[0036]
(7) Two-component emulsion approach that can build a three-dimensional crosslinked structure after coating formation
There is an approach to improve the durability (for example, solvent resistance, heat resistance, mechanical properties, adhesion, etc.) of the obtained coating film by using an emulsion capable of building a three-dimensional crosslinked structure after the coating film is formed.
In such an approach, an emulsion (crosslinkable emulsion) that can build a three-dimensional cross-linked structure after the formation of the coating film is applied to the base, when the coating film or film is formed, or after the coating film or film is formed. A three-dimensional crosslinked network structure is constructed by a crosslinking reaction, and a coating film or film having excellent durability (for example, solvent resistance, heat resistance, mechanical properties, adhesiveness, etc.) can be developed.
[0037]
Such a crosslinkable emulsion is classified into a one-pack type and a two-pack type depending on whether it is applied as it is or when the two liquids are mixed and then applied.
In the case of the two-pack type, there is no problem in the storage stability of the emulsion itself, but there is a problem that workability is poor because the two liquids are mixed before use.
Since the two liquids are reactive with each other, they are mixed before use. The two-component type has a problem because the pot life is short. Here, the pot life means the maximum time (usable time, pot life) from immediately after mixing to the end of the period when the mixture can be used. Even within the pot life time range, the viscosity of the two-component mixture increases with time, so the film-forming property, film-forming property or film-forming property decreases with time, and may be accompanied by this. The durability of the resulting coating film or film is also reduced.
When the two liquids are composed of liquid A and liquid B, the crosslinking reaction of the coating proceeds between the polymer particles and / or compound in liquid A and the polymer particles and / or compound in liquid B. As the viscosity increases, the viscosity effect (gel effect, diffusion rate limiting effect) increases, the reaction rate of the crosslinking reaction decreases extremely, and a non-negligible amount of reactive functional groups remain unreacted. .
[0038]
(8) One-component emulsion approach that can build a three-dimensional crosslinked structure after coating formation
There is the following one-component emulsion approach to solve the problems of the two-component emulsion.
i) A system using a crosslinking reaction between a carboxyl group and a hydrazide group
JP-A-59-131682 (Japanese Examined Patent Publication No. 62-14191, Daijiro Asai and Teruhiko Kondo) discloses a room-temperature-crosslinking acrylic polymer emulsion having a carbonyl group containing a hydrazine derivative and unmodified polyvinyl alcohol. Also disclosed is a technology relating to a one-component, water-dispersed adhesive that is excellent in workability and water-resistant adhesive strength, characterized by containing a modified polyvinyl alcohol having a carboxyl group or an amide group introduced therein in a specific ratio. ing.
JP-A-63-101435 (Japanese Patent Publication No. 4-55614, Naoto Abe et al.) Discloses that a plastic (polyolefin, polyethylene terephthalate, polystyrene, etc.) film is coated with a specific room temperature crosslinkable acrylic aqueous emulsion composition as a binder. A technique relating to coated paper, which is excellent in printability, writing property, and printability by applying a coating agent and has good adhesion between a base and a coating layer, is disclosed. Here, the specific room-temperature-crosslinking acrylic aqueous emulsion composition contains component (A); a hydrazine derivative having at least two hydrazine residues, component (B); and a carbonyl group-containing acrylic copolymer.
In principle, the film forming techniques disclosed in JP-A-59-131682 and JP-A-63-101435 utilize the crosslinking reaction between a carboxyl group and a hydrazide group.
[0039]
ii) System using cross-linking reaction between unsaturated double bond and amino group
JP-A-3-152168 (Yoshikazu Ishida and Masaki Nomura) describes an emulsion (A) and an emulsion (B) as an unsaturated double bond existing in the polymer molecule of (A) and a polymer molecule of (B). Disclosed is a technology related to an aqueous resin dispersion that can form a coating film, which is formulated with a specific equivalent ratio of active hydrogen present therein and has excellent adhesion, water resistance, solvent resistance, and weather resistance. Yes.
Here, the emulsion (A) contains polymer particles having an acryloyl unsaturated double bond in a specific molecule, and the emulsion (B) is a polymer particle having an amino group in a specific molecule. Is included.
[0040]
iii) System using cross-linking reaction between epoxy group and carboxyl group
Japanese Patent Application Laid-Open No. 57-65704 (Japanese Patent Publication No. 2-12964, Kunihide Tanabe et al.) Has two layers, a layer (A) and a layer (B), and both layers are crosslinked by reactive polar groups. A technique relating to a copolymer emulsion composition that can form a film containing structured particles and having high elasticity and excellent water resistance is disclosed.
Here, the layer (A) can serve as a core. The monomer (M1), that is, an α, β-ethylenically unsaturated monomer having a polar group in the molecule, and the monomer (M1) '), That is, a copolymer of an α, β-ethylenically unsaturated monomer having no polar group in the molecule.
Further, the layer (B) can be formed into a shell by being deposited on the core, and the polarity present in the monomer (M2), that is, in the molecule of the monomer (M1). Α, β-ethylenically unsaturated monomer having a polar group reactive to the group and monomer (M2 ′), ie, α, β-ethylenic having no polar group in the molecule It is a copolymer of an unsaturated monomer.
When polymerization is carried out while laminating layers (A) and (B) adjacent to each other, polar groups in the monomer (M1) residue present in layer (A) and layers (B) A cross-linking reaction takes place between the polar groups in the monomer (M2) residues present and a cross-linking bond is established between both layers.
Specific examples of the combination of the monomer (M1) and the monomer (M2) include epoxy derivatives / unsaturated carboxylic acids, vinylsilanes / methylol derivatives, and the like.
[0041]
According to the prior art relating to a one-component emulsion capable of constructing a three-dimensional cross-linked structure after the formation of the coating film as in i) to iii) above, the durability of the resulting coating film (for example, solvent resistance, heat resistance, Mechanical properties, adhesion, etc.) are significantly improved.
However, all of the conventional techniques based on such an approach are based on the technical idea of using particles having only organic polymers as constituent elements, and regarding the blocking resistance of the coating film formed by such techniques, The problem remained.
[0042]
[Problems to be solved by the invention]
However, as a result of intensive studies in view of various problems of various conventional water-dispersible coating compositions as described above, the present inventors have obtained a core / shell that can express a coating excellent in durability and blocking resistance. Particles, an emulsion containing water as a continuous phase with the particles as a dispersed phase, an aqueous dispersible composition having the characteristics of latex or suspension, an aqueous dispersible coating composition containing the aqueous dispersible composition as a main component, A manufacturing method has been found and the present invention has been completed.
[0043]
The approach by blending (6) “emulsion containing inorganic compound / alkoxysilane group-containing organic polymer particles” in the above prior art is based on the technical idea to hold inorganic compound by covalent bond with organic polymer. In this case, since the particles do not have a three-dimensional cross-linked structure, there are problems in durability (for example, solvent resistance, heat resistance, mechanical properties, adhesion, etc.), and reactivity with inorganic compounds. There has been a problem that the functional group having a tendency to cause gelation.
The approach by the one-component type emulsion that can construct a three-dimensional cross-linked structure after the formation of the coating film of the prior art (8) is based on a technical idea using particles having only an organic polymer as a constituent element. There was a problem regarding the blocking resistance of the coating film.
[0044]
In contrast to these prior arts, the present invention provides a core / shell structure of an organic polymer and an inorganic compound (silica) that are not covalently bonded to each other in the core, and the organic high content in the shell. By arranging molecules and forming a three-dimensional crosslinked network structure and / or IPN (inter-penetrating network) structure between the core organic polymer / shell organic polymer, the inorganic compound (silica) in the core is physically and chemically Excellent durability (solvent resistance, heat resistance, adhesion to substrate, water resistance), excellent physics when the film is formed by holding or containment, MFT (minimum film formation temperature) or higher Gives properties (elasticity, elongation properties, toughness), excellent anti-blocking properties, excellent appearance properties (smoothness, sharpness, etc.), and high organic content without covalent bonding of inorganic compounds It is novel in that it is based on the technical idea that it is retained or contained in the film by physicochemical and / or secondary bonds (hydrogen bonds, hydrophobic bonds, van der Waals bonds, etc.) due to the network structure of the child. Have.
[0045]
[Means for Solving the Problems]
The present invention is the invention described in the following (1) to (12).
(1) Core / shell structure, organic polymer and silica and / or colloidal silica that are not covalently bonded to the organic polymer are arranged in the core, and the organic polymer is arranged in the shell. By forming a three-dimensional crosslinked network structure and / or IPN (inter-penetrating network) structure between the / shell organic polymers, the silica and / or colloidal silica in the core is physicochemically held in the particle without being covalently bonded. Particles.
[0046]
(2) Core / shell structure, silica and / or colloidal silica that is not covalently bonded to organic polymer and organic polymer are arranged in the core, and organic polymer is arranged in the shell. By forming a three-dimensional crosslinked network structure and / or IPN (inter-penetrating network) structure between the / shell organic polymers, the silica and / or colloidal silica in the core is physicochemically held in the particle without being covalently bonded. In addition, when a film is formed at a temperature higher than the Tg (glass transition point) of the particle or the MFT (minimum film forming temperature) of the composition containing the particle, the silica and / or colloidal silica is physically and chemically incorporated into the film without being covalently bonded. Particles that have a function of holding and forming a film excellent in durability, physical properties, blocking resistance, and appearance properties.
[0047]
(3) As the core monomer (c1), a monomer having an epoxy group and an unsaturated double bond in the molecule, and having no functional group reactive with the epoxy group and no alkoxysilane group in the molecule At least one monomer selected from the group consisting of ethylenically unsaturated monomers,
As the core monomer (c2), a monoethylenic group having an unsaturated double bond in the molecule and not having a functional group reactive with an epoxy group, an epoxy group or an alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers, and
As the core colloidal silica (c3), at least one kind of colloidal silica,
Having a core (C) obtained by polymerization in a reaction system containing
As the shell monomer (s1), a monoethylenic group having an unsaturated double bond and a functional group reactive with an epoxy group in the molecule and no epoxy group or alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers, and
As the shell monomer (s2), a monoethylenic group having an unsaturated double bond in the molecule and having no functional group reactive with the epoxy group, epoxy group or alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers,
Particles having at least one shell (S) obtained by polymerization in a reaction system containing
[0048]
(4) As the core monomer (c1), a monomer having an unsaturated double bond and a functional group reactive with an epoxy group in the molecule, and having no epoxy group or alkoxysilane group in the molecule At least one monomer selected from the group consisting of ethylenically unsaturated monomers, and
As the core monomer (c2), a monoethylenic group having an unsaturated double bond in the molecule and not having a functional group reactive with an epoxy group, an epoxy group or an alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers,
As the core colloidal silica (c3), at least one kind of colloidal silica,
Having a core (C) obtained by polymerization in a reaction system containing
As the shell monomer (s1), a monoethylenic group having an epoxy group and an unsaturated double bond in the molecule, and a functional group reactive with the epoxy group and an alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers, and
As the shell monomer (s2), a monoethylenic group having an unsaturated double bond in the molecule and having no functional group reactive with the epoxy group, epoxy group or alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers,
Particles having at least one shell (S) obtained by polymerization in a reaction system containing
[0049]
(5) A monoethylenically unsaturated monomer having an unsaturated double bond in the molecule used for polymerizing the core (C) and an unsaturated double bond used for polymerizing the shell (S). (1) to (4), wherein the core / colloidal silica (c3) is 1 to 100 parts by weight with respect to 100 parts by weight of the total weight of the monoethylenically unsaturated monomers in the molecule. Particles described in any of the above.
[0050]
(6) Monoethylenically unsaturated monomer having an unsaturated double bond in the molecule used for polymerizing the core (C) and unsaturated double bond used for polymerizing the shell (S) The particle according to any one of (1) to (4), wherein the weight ratio of the monoethylenically unsaturated monomer contained therein is 5:95 to 90:10.
[0051]
(7) The particle according to any one of (1) to (6), wherein the core colloidal silica (c3) is a water dispersion type.
(8) A water-based dispersible composition having the characteristics of emulsion, latex or suspension, comprising the particles described in any one of (1) to (7) as a dispersed phase and water as a continuous phase.
[0052]
(9) An aqueous dispersible coating composition comprising the aqueous dispersible composition described in (8) as a main component.
(10) As step 1 (core particle forming step), in an aqueous continuous phase containing a radical polymerization initiator,
As the core monomer (c1), a monoethylenic group having an epoxy group and an unsaturated double bond in the molecule, and a functional group reactive with the epoxy group and an alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers,
As the core monomer (c2), a monoethylenic group having an unsaturated double bond in the molecule and not having a functional group reactive with an epoxy group, an epoxy group or an alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers, and
As the core colloidal silica (c3), at least one kind of colloidal silica,
Carrying out emulsion polymerization or suspension polymerization at a temperature of about 10 ° C. to about 100 ° C., thereby forming dispersed core particles;
In step 2 (shell formation step), in the aqueous continuous phase containing the radical polymerization initiator in which the core polymer obtained in step 1 (core particle formation step) is dispersed,
As the shell monomer (s1), a monoethylenic group having an unsaturated double bond and a functional group reactive with an epoxy group in the molecule and no epoxy group or alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers, and
As the shell monomer (s2), a monoethylenic group having an unsaturated double bond in the molecule and having no functional group reactive with the epoxy group, epoxy group or alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers,
Carrying out emulsion polymerization or suspension polymerization at a temperature of about 10 ° C. to about 100 ° C. to thereby form core / shell particles,
And in which step 1 and step 2 are related by continuous emulsion polymerization or suspension polymerization, and the relative amount of core-forming monomer and shell-forming monomer is the core polymer in the resulting particles Emulsion comprising water-insoluble core / shell polymer particles as a dispersed phase and water as a continuous phase, wherein the ratio of weight to shell polymer weight is from 5:95 to 90:10 , A method for producing an aqueous dispersion having the characteristics of latex or suspension.
[0053]
(11) As step 1 (core particle forming step), in an aqueous continuous phase containing a radical polymerization initiator,
As the core monomer (c1), a monoethylenic group having an unsaturated double bond and a functional group reactive with an epoxy group in the molecule and no epoxy group or alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers,
As the core monomer (c2), a monoethylenic group having an unsaturated double bond in the molecule and not having a functional group reactive with an epoxy group, an epoxy group or an alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers, and
As the core colloidal silica (c3), at least one kind of colloidal silica,
Carrying out emulsion polymerization or suspension polymerization at a temperature of about 10 ° C. to about 100 ° C., thereby forming dispersed core particles;
In step 2 (shell formation step), in the aqueous continuous phase containing the radical polymerization initiator in which the core polymer obtained in step 1 (core particle formation step) is dispersed,
As the shell monomer (s1), a monoethylenic group having an epoxy group and an unsaturated double bond in the molecule, and a functional group reactive with the epoxy group and an alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers, and
As the shell monomer (s2), a monoethylenic group having an unsaturated double bond in the molecule and having no functional group reactive with the epoxy group, epoxy group or alkoxysilane group in the molecule. At least one monomer selected from the group consisting of saturated monomers,
Carrying out emulsion polymerization or suspension polymerization at a temperature of about 10 ° C. to about 100 ° C. to thereby form core / shell particles,
And in which step 1 and step 2 are related by continuous emulsion polymerization or suspension polymerization, and the relative amount of core-forming monomer and shell-forming monomer is the core polymer in the resulting particles Emulsion comprising water-insoluble core / shell polymer particles as a dispersed phase and water as a continuous phase, wherein the ratio of weight to shell polymer weight is from 5:95 to 90:10 , A method for producing an aqueous dispersion having the characteristics of latex or suspension.
(12) An aqueous dispersion produced by the production method according to (10) or (11).
[0054]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the aspect of the particles according to the present invention include the following aspects (1) and (2).
(1) A shell type particle having a functional group having reactivity with a core / epoxy group having an epoxy group.
(2) Shell-type particles having a core / epoxy group having a functional group reactive with an epoxy group.
The above aspects (1) and (2) are as follows.
[0055]
(1) Core-type particles having epoxy groups / shell-type particles having functional groups reactive with epoxy groups
A core monomer (c1); at least one monomer having at least one epoxy group and at least one unsaturated double bond in the molecule and having no alkoxysilane group in the molecule;
A core monomer (c2); having at least one unsaturated double bond in the molecule and not having a functional group reactive with an epoxy group, an epoxy group and an alkoxysilane group in the molecule; One monomer, and
Core colloidal silica (c3); at least one colloidal silica;
Having a core (C) obtained by polymerization in a reaction system containing
Shell monomer (s1); having at least one unsaturated double bond and at least one functional group reactive with an epoxy group in the molecule, and having an epoxy group and an alkoxysilane group in the molecule At least one monomer, and
Shell monomer (s2); having at least one unsaturated double bond in the molecule and not having a functional group reactive with an epoxy group, an epoxy group and an alkoxysilane group in the molecule, One kind of monomer,
Particles having at least one shell (S) obtained by polymerization in a reaction system containing
[0056]
(2) Shell type particles having a core / epoxy group having a functional group reactive with an epoxy group
Core monomer (c1); having at least one unsaturated double bond and at least one functional group reactive with an epoxy group in the molecule, and having an epoxy group and an alkoxysilane group in the molecule At least one monomer,
A core monomer (c2); having at least one unsaturated double bond in the molecule and not having a functional group reactive with an epoxy group, an epoxy group and an alkoxysilane group in the molecule; One monomer, and
Core colloidal silica (c3); at least one colloidal silica;
Having a core (C) obtained by polymerization in a reaction system containing
Shell monomer (s1); at least one monomer having at least one epoxy group and at least one unsaturated double bond in the molecule and having no alkoxysilane group in the molecule; as well as,
Shell monomer (s2); having at least one unsaturated double bond in the molecule and not having a functional group reactive with an epoxy group, an epoxy group and an alkoxysilane group in the molecule, One kind of monomer,
Particles having at least one shell (S) obtained by polymerization in a reaction system containing
[0057]
Hereinafter, the present invention will be described in detail.
Monomer A: a monomer having at least one epoxy group and at least one unsaturated double bond in the molecule and having no alkoxysilane group in the molecule
Specific examples of a monomer having at least one epoxy group and at least one unsaturated double bond in the molecule and having no alkoxysilane group in the molecule (hereinafter referred to as monomer A) Glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, N-glycidyl acrylate amide, allyl glycidyl ether, glycidyl vinyl sulfonate, and the like. Among them, glycidyl acrylate and glycidyl methacrylate are used. Preferably, these can be used alone or in combination of two or more.
[0058]
In general, the amount of the monomer A used is preferably 0.1 to 40% by weight, more preferably 3 to 20% by weight, based on all monomers.
When the amount of monomer A used is reduced to 0.1% by weight or less, the crosslinking density decreases accordingly, and the resulting coating film also has a crosslinking density, impact resistance, and water resistance. There is a tendency that physical properties of the coating film such as solvent resistance are lowered.
On the other hand, when the amount of the monomer A used is increased to 40% by weight or more, the reaction stability of the polymerization itself is lowered due to an undesirable side reaction. Gelation is likely to occur during the reaction between the epoxy group and the functional group having reactivity with the epoxy group, and the appearance characteristics such as smoothness and sharpness of the resulting coating film tend to decrease. It is done.
[0059]
Monomer B: a monomer having at least one unsaturated double bond in the molecule and having no functional group reactive with the epoxy group, epoxy group or alkoxysilane group in the molecule
Monomer having at least one unsaturated double bond in the molecule and having no functional group reactive with the epoxy group, epoxy group and alkoxysilane group in the molecule (hereinafter referred to as monomer B) Specific examples of such as) are ethylenically unsaturated carboxylic acids having a carboxyl group in the molecule, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, N-methylaminoethyl acrylate, N-methylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc. acrylic acid or methacrylic acid alkylamino esters having amino groups in the molecule, monovinylpyridines such as vinylpyridine, dimethylaminoethyl vinyl ether, etc. Vinyl ether having an alkylamino group in the molecule And unsaturated amides having an alkylamino group in the molecule such as N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide, and the like. Or two or more types can be used in combination.
[0060]
In general, the amount of the monomer B used is preferably 0.1 to 40% by weight, more preferably 3 to 20% by weight, based on all monomers.
The relative ratio of the monomer A and the monomer B exists in the polymer molecule having an epoxy group in consideration of the reaction between the epoxy group and the functional group having reactivity with the epoxy group between the core and the shell. The equivalent of the functional group having reactivity with the epoxy group present in the polymer molecule having a functional group reactive with the epoxy group is equivalent to 0.5 to 2 equivalents with respect to 1 equivalent of the epoxy group. It is preferable to do so.
When the amount of the monomer B used is reduced to 0.1% by weight or less, the crosslinking density decreases accordingly, and the resulting coating film also has a crosslinking density, impact resistance, and water resistance. There is a tendency that physical properties of the coating film such as solvent resistance are lowered.
On the other hand, when the amount of the monomer B used is increased to 40% by weight or more, the reaction stability of the polymerization itself is lowered due to an undesirable side reaction, and the epoxy group between the core and the shell is reduced. Gelation is likely to occur during the reaction between the epoxy group and the functional group having reactivity with the epoxy group, and the appearance characteristics such as smoothness and sharpness of the resulting coating film tend to decrease. It is done.
[0061]
Monomer C: a monomer having at least one unsaturated double bond in the molecule and having no functional group reactive with the epoxy group, epoxy group or alkoxysilane group in the molecule
Monomer having at least one unsaturated double bond in the molecule and having no functional group reactive with the epoxy group, epoxy group and alkoxysilane group in the molecule (hereinafter referred to as monomer C As specific examples, methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, sec-butyl-, tert-butyl-, n-amyl-, isoamyl-, n -Hexyl-, cyclohexyl-, 2-ethylhexyl-, octyl-, 2-ethyloctyl-, decyl-, dodecyl-, octadecyl-, stearyl-, cyclohexyl-, benzyl-, phenyl-, hydroxyethyl-, 2-hydroxypropyl -, 3-hydroxypropyl-, 2-hydroxybutyl-, 3-hydroxybutyl-, 4-hydroxybutyl-, polyethylene Acrylic acid derivatives or methacrylic acid derivatives including acrylic acid esters or methacrylic acid esters such as N-glycol mono-, 1,4-butanediol mono-, dimethylamino-, esters of dicarboxylic acids such as maleic acid and itaconic acid, vinylamides Amides such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, diacetone acrylamide, diacetone methacrylamide, etc., and these may be used alone or in combination of two or more. Can do.
[0062]
Other specific examples of the monomer C include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene and other aromatic vinyls, vinyl chloride, vinylidene chloride. , Halogenated ethylenically unsaturated monomers such as vinyl fluoride, monochlorotrifluoroethylene, tetrafluoroethylene and chloroprene, nitriles such as acrylonitrile and methacrylonitrile, vinyl esters such as vinyl acetate and vinyl propionate, ethylene Ethylene, propylene, isoprene, butadiene, α-olefins such as α-olefins having 4 to 20 carbon atoms, alkyl vinyl ethers such as lauryl vinyl ether, nitrogen-containing vinyls such as vinylpyrrolidone and 4-vinylpyrrolidone, etc. Emissions unsaturated monomer and the like, which may be used alone or in combination of two or more.
[0063]
Colloidal silica concept
The concept of the term “colloidal silica” used in the claims and the specification of the present application is the “colloid” in the right column of pages 738 to 739 of the Chemical Dictionary, Volume 3 (Kyoritsu Shuppan, Tokyo, 1963). Including the concept described in the section “Silica (colloidal silica)”. The description is taken as a matter or disclosure that can be derived directly and unambiguously by those skilled in the art from the matter or disclosure described in the specification of the present application by reference.
Further, the concept of the term “colloidal silica” used in the claims and the specification of the present application is the same as that of 12695 chemical products (Chemical Industry Daily, Tokyo, 1995), page 95, left column to right column. It also encompasses the concept described in the section “Colloidal silica”.
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
[0064]
The concept of the term “silica” used in the claims and the specification of the present application is the term “silica” in the left column of 870 pages of Chemistry Dictionary, Volume 4 (Kyoritsu Shuppan, Tokyo, 1963). And the concept described in the section of “silicon dioxide” in the left column of page 696 to the left column of page 697 (Kyoritsu Shuppan, Tokyo, 1963).
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
[0065]
Colloidal silica particle size and colloidal pH
The particle size of the anhydrous silicic acid ultrafine particles constituting the colloidal silica is, for example, about 4 to 100 nanometers, or about 10 to 20 nanometers.
Colloidal liquid of colloidal silica is, for example, SiO ₂ XH ₂ As long as it contains O as a dispersed phase and water as a continuous phase, and its pH can maintain a substantially stable colloidal liquid (aqueous dispersion) during use, the acidic side or basic side Any of these may be used.
[0066]
Water-dispersed colloidal silica
The water-dispersed colloidal silica has a colloidal form in which negatively charged amorphous silica particles are dispersed in water, and there are an acidic side and a basic side.
Specific examples of the acidic colloidal silica include Snowtex O and OL (manufactured by Nissan Chemical Industries, Ltd.).
Specific examples of the basic colloidal silica include Snowtex XS, XL, 20, 30, 40, 50, C, N, S and 20L (manufactured by Nissan Chemical Industries, Ltd.).
Acid side or base side colloidal silica is also marketed by Asahi Denka Co., Ltd., Catalytic Chemical Industry Co., Ltd., Nippon Chemical Co., Ltd., DuPont, Narco Chemical Co., etc.
[0067]
Various conditions of colloidal silica (c3) used in the present invention (silica particle size / size distribution, colloidal solution pH, etc.) are substantially efficiently and stably incorporated into the core when preparing the core. There is no particular limitation as long as it is.
When colloidal silica is used in emulsion polymerization or suspension polymerization, a desired product can be prepared by appropriately selecting various conditions (particle size / size distribution of silica particles, pH of colloidal liquid, etc.). .
[0068]
Colloidal silica used in the present invention
Preferable examples of colloidal silica (c3) used in the present invention include water-dispersed type.
The average particle diameter of the colloidal silica (c3) used in the present invention is preferably, for example, 1 to 100 nanometers, and more preferably 4 to 50 nanometers.
The amount of colloidal silica (c3) used in the present invention is not particularly limited as long as it is incorporated into the core substantially efficiently and stably when preparing the core.
The amount of colloidal silica (c3) used in the present invention is preferably 1 to 100 parts by weight, and more preferably 2 to 50 parts by weight with respect to 100 parts by weight of the total weight of the organic polymer present in the core.
[0069]
Aspect of particles having a core / shell structure composed of A layer / B layer
In an embodiment of the particles according to the present invention, the particles constituting the dispersed phase of the emulsion have a core / shell structure composed of A layer / B layer.
A layer (core)
In the above embodiment, the layer A (core) comprises the core monomer (c1); an ethylenically unsaturated monomer having an epoxy group, the core monomer (c2); an epoxy group that is not reactive with the epoxy group. It is obtained by polymerizing in a reaction system containing an ethylenically unsaturated monomer having no carbon and core / colloidal silica (c3); colloidal silica.
[0070]
B layer (shell)
In the above embodiment, the layer B (shell) comprises a shell monomer (s1); an ethylenically unsaturated monomer that is reactive with an epoxy group and has no epoxy group; and a shell monomer (s2) Obtained by polymerization in a reaction system containing an ethylenically unsaturated monomer that is not reactive with epoxy groups and has no epoxy.
[0071]
Aspect of preparation of particles having a core / shell structure composed of A layer / B layer
The particle | grains of the said aspect can be prepared as follows, for example.
First, a predetermined amount of colloidal silica (c3), a surfactant, and pure water are charged into a reaction vessel.
Next, the core monomer (c1); the ethylenically unsaturated monomer having an epoxy group, and the core monomer (c2); the epoxy group having no reactivity with the epoxy group, which forms the layer A Polymerization is performed by adding a mixed solution of ethylenically unsaturated monomers having no diol at once or continuously dropwise.
Next, after the polymer of layer A is obtained, shell monomer (s1) that forms layer B, ethylenically unsaturated monomer that is reactive with epoxy groups and has no epoxy groups, And a mixture of a shell monomer (s2); an ethylenically unsaturated monomer that is not reactive with an epoxy group and has no epoxy, is polymerized by batch addition or continuous dropwise addition, and layer A / B Particles having a core / shell structure consisting of layers can be obtained. Here, the ethylenically unsaturated monomer may be mixed in advance with pure water and a surfactant to form an emulsion.
[0072]
Weight ratio of organic polymer of A layer (core) / B layer (shell)
In the said aspect, it is preferable that the ratio of the total weight of the organic polymer which exists in each of A layer and B layer is 5 to 95 to 90 to 10.
As the weight ratio departs from the above preferred numerical range, the degree of cross-linking between the core and the shell decreases, and the cross-linking density of the film when the film is formed also decreases. Accordingly, the solvent resistance and water resistance of the film are reduced. There is also a tendency for the performance to decline.
[0073]
Tg and particle size of organic polymer of A layer (core) / B layer (shell)
In the above embodiment, it is preferable to design the molecules so that the Tg of each of the A layer and the B layer is -50 to 100 ° C.
In the above aspect, the core / shell type particles preferably have a particle size in the range of 50 to 500 nanometers.
By making the particle diameter of the core / shell type particles or the particle diameter of silica (including colloidal silica) larger than the wavelength of visible light or sunlight, the opaque material is made opaque by scattering light rays. It is also possible to apply particles to the agent.
As the particle diameter is reduced to 50 nanometers or less, the viscosity of the emulsion becomes very high, the workability during use tends to decrease, and the specific surface area of the particles also increases. As a result, the stability of the emulsion itself tends to decrease.
On the other hand, as the particle size is increased to 500 nanometers or more, the film forming ability tends to decrease, and the water resistance and solvent resistance tend to decrease.
[0074]
Non-volatile content weight% of aqueous composition containing particles according to the present invention
The non-volatile content by weight of the water-based dispersible composition according to the present invention or the water-based dispersible coating composition containing the water-based dispersible composition as a main component is substantially constant so that the composition system is continuously stable. There is no particular limitation as long as the storage stability and workability are substantially ensured substantially.
The non-volatile content weight% of the aqueous dispersible composition according to the present invention or the aqueous dispersible coating composition containing the aqueous dispersible composition as a main component is preferably, for example, 20 to 60%.
In a certain aspect, when the non-volatile matter weight% is reduced to 20% or less, the thickness of the coating tends to become thin when the coating is formed, and the working efficiency tends to decrease accordingly. It is done.
On the other hand, in one aspect, when the non-volatile matter weight% is increased to 60% or more, the viscosity of the composition tends to increase, and the workability tends to decrease accordingly. , The stability during polymerization or composition preparation tends to be reduced or gelled.
[0075]
Method for preparing particles according to the present invention
The method for preparing particles according to the present invention is a means capable of substantially realizing desired particle characteristics (layer structure, non-hollow structure, hollow structure, form, particle size, particle size distribution, single aspect / multi-form, etc.). If it is, it will not be restrict | limited.
The particles according to the present invention can be preferably prepared by an emulsion polymerization method, but can also be prepared by a suspension polymerization method.
[0076]
Surfactant
The surfactant used in the method for producing an aqueous dispersion according to the present invention forms a dispersed phase containing a monomer or colloidal silica in a continuous aqueous phase substantially continuously and stably. If there is no particular limitation.
As the surfactant used in the method for producing an aqueous dispersion according to the present invention, known surfactants used in usual emulsion polymerization may be used alone or in combination.
Specific examples of the nonionic surfactant, the anionic surfactant, and the cationic surfactant are listed below, but these can be suitably used alone or in combination.
[0077]
Anionic surfactant
Specific examples of the anionic surfactant used in the method for producing an aqueous dispersion according to the present invention include sodium dodecylbenzene sulfonate (DBS, SDS), sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalene sulfonate. Sodium dialkyl sulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sodium sodium dialkyl sulfosuccinate, stearin Acid sodium, sodium oleate, tert-octylphenoxyethoxypoly- (40)- Tokishiechiru sodium sulfate, and the like. These may be used singly or as a mixture.
[0078]
Nonionic surfactant
Specific examples of the nonionic surfactant used in the method for producing an aqueous dispersion according to the present invention include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether, Examples thereof include oxyethylene / oxypropylene block copolymer, tert-octylphenoxyethyl poly- (39) -ethoxyethanol, nonylphenoxyethyl poly- (40) -ethoxyethanol and the like, which can be used alone or in combination. .
[0079]
Cationic surfactant
Specific examples of the cationic surfactant used in the method for producing an aqueous dispersion according to the present invention include lauryltrimethylammonium chloride and stearyltrimethylammonium chloride, and these can be used alone or in combination.
[0080]
Amount of surfactant used during seed polymer polymerization
The amount of the surfactant used in the method for producing an aqueous dispersion according to the present invention is an amount that substantially forms micelles in the reaction system, or a dispersed phase containing a monomer or colloidal silica in the aqueous continuous phase. Is not particularly limited as long as it is an amount that can be formed stably, stably and uniformly.
In general, the type and concentration of the surfactant are determined depending on the desired particle characteristics (layer) while taking into account the CMC (critical micelle formation concentration) value unique to the surfactant and the HLB (hydrophilic hydrophobic balance) value. Structure, hollow structure, form, particle size, particle size distribution, single aspect / polymorphism, etc.) can be appropriately selected.
In one embodiment, the surfactant may be used in an amount of 0.1 to 10% by weight based on the total weight of all monomers supplied to the reaction system.
In such an embodiment, when the amount of the surfactant used is decreased to 0.1% by weight or less, the polymerization stability is lowered and a tendency to be easily gelled during the polymerization is observed.
On the other hand, when the amount of the surfactant used is increased to 10% by weight or more, the water resistance of the coating tends to decrease when the coating is formed.
In another embodiment using a persulfate polymerization initiator, the amount of the surfactant used is 0 to 2.0% by weight based on the total weight of all the monomers present in the reaction system. Can be used.
[0081]
Surfactant usage in multistage continuous polymerization.
In an embodiment using a persulfate polymerization initiator, the amount of surfactant used is 0 to 2.0% by weight, based on the total weight of all monomers fed in the first stage of polymerization. I just need it.
By conducting emulsion polymerization while maintaining a low level of surfactant usage, the continuous stage of polymer formation is the result of existing dispersed polymer particles obtained by producing the most recently formed polymer in the previous stage. Can be deposited on top.
Here, “emulsion polymerization is performed while maintaining the amount of surfactant used at a low level” generally means that the amount of surfactant used in the reaction system at that stage is greater than the amount corresponding to the CMC value. Also means keeping it low.
[0082]
Such a limitation of the condition that “emulsion polymerization is carried out while maintaining the amount of surfactant used at a low level” is generally preferable, and for obtaining a monomorphic product. In some embodiments of the reaction system, the amount of dispersed micelles or granules having desirable properties or a non-excessive amount, even when a surfactant equivalent to or higher than the CMC value is used, is used. It has been found to involve generation.
Such limitation of the condition of “performing emulsion polymerization while keeping the amount of surfactant used at a low level” controls the number of micelles in each stage of multi-stage continuous polymerization. This has the effect of depositing the polymer produced in that stage on the granules or micelles produced in that stage.
[0083]
Polymerization temperature
The polymerization temperature employed in the method for producing an aqueous dispersion according to the present invention is not particularly limited as long as the polymerization reaction proceeds substantially sufficiently.
The polymerization temperature is set in consideration of the type of monomer to be used, the type of polymerization initiator, and the like. Generally, a temperature range of about 10 to about 100 ° C. is preferable, and a temperature of about 30 to about 90 ° C. A range is more preferred.
Suitable polymerization temperatures for various polymerization initiators are, for example, Chemical Monograph Vol. 15: Chemistry of Polymer Synthesis (Takayuki Otsu, Kagaku Dojin, Kyoto, 1968) p. 63, Table 3-2 “Initiator Classification In the method for producing an aqueous dispersion according to the present invention, such conditions can be suitably employed.
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
When a persulfate polymerization initiator is used, a temperature range of about 60 to about 90 ° C. is generally preferred.
When a redox polymerization initiator is used, a temperature range of about 30 to about 70 ° C. is generally preferable, a temperature range of about 30 to about 60 ° C. is more preferable, and a temperature range of about 30 to about 45 ° C. Is more preferable.
[0084]
Type of polymerization initiator
Specific examples of the polymerization initiator used in the method for producing an aqueous dispersion according to the present invention include hydrogen peroxide, tertiary butyl peroxide, ammonium persulfate, alkali metal persulfate (metal: sodium, potassium or lithium). Water-soluble free radical initiation commonly used in emulsion polymerization, such as sulfates, azo compounds such as azobisisobutyronitrile, and organic peroxides such as cumene hydroperoxide and tert-butyl hydroperoxide Agents, which can be used alone or as a mixture.
Other specific examples of the polymerization initiator include an oxidation-reduction (redox) polymerization initiator that forms a redox system by using a reducing agent together with the polymerization initiator.
[0085]
Examples of the reducing agent include sulfites such as metabisulfite, hydrosulfite, and alkali metal hyposulfite, metal ions such as sodium formaldehyde sulfoxylate, sodium pyrosulfite, L-ascorbic acid, and iron ions. Or it can be used as a mixture.
In the method for producing an aqueous dispersion according to the present invention, for example, Chemical Monograph Vol. 15, Chemistry of Polymer Synthesis (Takayuki Otsu, Kagaku Dojin, Kyoto, 1968) 62-72, “Initiation of radical polymerization Those listed in the section of “Agent” can be preferably used alone or as a mixture.
All the descriptions are made a part of the disclosure of the present application specification by specifying the cited references and the reference range, and in view of the matters or disclosure described in the specification of the present application by referring to the specified reference range. Matters or disclosure that can be derived directly and unambiguously by the contractor.
[0086]
Amount of polymerization initiator used
The amount of the polymerization initiator used in the method for producing an aqueous dispersion according to the present invention is not particularly limited as long as the reaction rate can be substantially secured.
In general, the amount of the polymerization initiator used is preferably in the range of 0.01 to 4 parts by weight with respect to 100 parts by weight of the total weight of monomers to be supplied.
In addition, the amount of the reducing agent used in the oxidation-reduction (redox) system is preferably in the range of 0.01 to 4 parts by weight with respect to 100 parts by weight of the total weight of the supplied monomers.
The addition method of the polymerization initiator may be batch addition or continuous addition.
[0087]
Molecular weight of the polymer produced in each stage of multistage continuous polymerization
The weight average molecular weight of the polymer produced in each stage of the multistage continuous polymerization is generally about 3,000,000 to about 100,000, and about 100,000 when a chain transfer agent is used. It is as follows. If crosslinking occurs in the course of polymerization, the molecular weight of the polymer can increase significantly.
For example, in certain embodiments where a relatively low weight average molecular weight, such as about 500,000 to about 20,000, is desired, the amount of monoethylenically unsaturated monomer used is suppressed, and a chain transfer agent is used instead. Use 0.05 to 2% or more.
[0088]
Chain transfer agent
In the method for producing an aqueous dispersion according to the present invention, a chain transfer agent such as mercaptans can be used as necessary.
Specific examples of the chain transfer agent include lower alkyl mercaptans such as sec-butyl mercaptan, and these can be used alone or in combination.
[0089]
Particle size
The average diameter of the particles according to the present invention is not particularly limited as long as the composition system is continuously stable and uniform, and the storage stability and workability are substantially ensured substantially.
In general, the average diameter of the core / shell particles according to the present invention is preferably in the range of 50 to 500 nanometers.
By making the particle diameter of the core / shell type particles or the particle diameter of silica (including colloidal silica) larger than the wavelength of visible light or sunlight, the opaque material is made opaque by scattering light rays. It is also possible to apply particles to the agent.
As the particle size is reduced to 50 nanometers or less, the viscosity of the emulsion becomes very high, and the workability during use tends to decrease, and the specific surface area of the particles also increases. As a result, the stability of the emulsion itself tends to decrease.
On the other hand, as the particle size is increased to 500 nanometers or more, the film forming ability tends to decrease, and the water resistance and solvent resistance of the film tend to decrease.
[0090]
Core polymer / shell polymer weight ratio
The weight ratio of the core polymer / shell polymer of the core / shell type particle according to the present invention is not particularly limited as long as the desired core / shell structure can be substantially secured.
The core polymer / shell polymer weight ratio of the core / shell particles according to the present invention is generally preferably 5:95 to 90:10.
[0091]
Additive
In the water-based dispersible composition or the water-based dispersible coating composition according to the present invention, additives that are used in ordinary polymer emulsion compositions can be added as necessary.
Specific examples of additives include, for example, antifoaming agents, dispersants, thickeners, pigments, pigment dispersants, bath agents, film-forming aids, organic solvents, plasticizers, antiseptics, antibacterial agents, and rust prevention. Agents, thixotropic agents (additives that suppress thixotropy or thixotropy) and the like, and these can be used alone or in combination.
[0092]
Base (substrate, substrate)
The water-based dispersible composition or water-based dispersible coating composition according to the present invention is subjected to primer or primer treatment on any base such as wood, paper, synthetic resin, glass, metal, ceramics, gypsum, or leather. And a preferable film can be formed. In addition, the composition can effectively form a coating on an inorganic substrate such as lightweight concrete, lightweight cellular concrete, mortar, asbestos cement board, calcium silicate board, gypsum board, or slate.
[0093]
In the specification of the present application, the examples, production examples, and modes are for supporting the understanding of the contents of the invention according to the present application, and the present invention is not limited in any way by the description. .
In order to describe the present invention more specifically, examples and comparative examples will be described below.
“Parts” and “%” used in the following description mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.
[0094]
【Example】
[Test method]
(1) Film creation
The aqueous dispersion composition was applied onto a glass plate and dried at 60 ° C. for 8 hours to produce a film.
Since the Tg of the particles or the MFT of the aqueous dispersion composition is high, those that do not form a film at 60 ° C. have 2,2,4-trimethyl-1,3 as a film-forming auxiliary so as to form a film at 60 ° C. , -Pentanediol monoisobutyrate was added to form a film.
This film was subjected to a water resistance test and a solvent resistance test.
[0095]
(2) Water resistance test
The film was immersed in water for 24 hours, and the whitening state of the film was visually observed.
The evaluation of the whitening state was based on the following three-stage criteria.
i) ◎; Good. No whitening at all. (Score = 5 points)
ii) ○: Normal. Some whitening. (Score = 3 points)
iii) x: Defect. Completely whitening. (Score = 0 points)
That is, the results are good in the order of ◎>○> ×.
[0096]
(3) Solvent resistance test
The film was immersed in toluene for 1 hour, and the area expansion coefficient was measured.
The solvent resistance was evaluated according to the following formula.
Solvent resistance (%) = (Area of film after immersion) / (Area of film before immersion)
The evaluation of adhesion was based on the following five-stage criteria.
i) <400; excellent. (Score = 5 points)
ii) <600; (Score = 4 points)
iii) <800; (Score = 3 points)
iv) <1000; bad. (Score = 2 points)
v) Dissolution; not possible. (Score = 0 points)
[0097]
(4) Adhesion test
The aqueous dispersion composition was applied onto a slate plate and dried at 60 ° C. for 8 hours to prepare a coating film.
Since the Tg of the particles or the MFT of the aqueous dispersion composition is high, those that do not form a film at 60 ° C. have 2,2,4-trimethyl-1,3 as a film-forming auxiliary so as to form a film at 60 ° C. , -Pentanediol monoisobutyrate was added to form a coating film.
Twenty-five 2-mm grids were made on this coating with a razor and a tape was affixed.
By peeling off the affixed tape, the number of grids remaining without peeling off the coating was counted.
The evaluation of adhesion was based on the following formula (the initial number of grids is 25).
Adhesion (%) = (Number of non-peeling cross-cuts) / (Number of initial cross-cuts) × 100
The evaluation of adhesion was based on the following four-stage criteria.
i) ◎; ≦ 100% (Score = 5 points)
ii) ○; <80% (score = 4 points)
iii) △; <60% (score = 2 points)
iv) ×; <40% (score = 0 points)
[0098]
(5) Blocking resistance test
Preparation of sample: The aqueous dispersion composition was applied to commercially available high-quality paper with a bar coater # 20, dried at 120 ° C. for 30 seconds, and then cut into a 10 cm × 10 cm square to prepare a sample.
Blocking resistance test: Aged for 4 hours in an atmosphere at a temperature of 80 ° C. and a relative humidity of 90%. Subsequently, the coated surfaces were combined and allowed to stand for 24 hours under a load of 30 kg. Thereafter, the degree of fusion (blocking property) was visually observed.
The evaluation of blocking resistance was based on the fusing property of the following formula.
Fusion property (%) = (Fused area) / (Total area) × 100
The evaluation of adhesion was based on the following four-stage criteria.
The evaluation of blocking resistance was based on the following four levels.
i) ◎; 0%; excellent. Not fused at all. (Score = 5 points)
ii) ○; ≦ 20%; normal. Partially fused. (Score = 3 points)
iii) Δ;>20%; poor. Partially fused. (Score = 1 point)
iv) x; 100%; Fully fused together. (Score = 0 points)
That is, the results are good in the order of ◎ >＞>Δ> ×.
Evaluation was made in three stages.
[0099]
(6) Overall evaluation
Comprehensive evaluation was based on the following four levels, based on the total score in the four-item evaluation.
However, if even one item has a score of 0 points, the overall evaluation is x (impossible).
i) ◎; (Total score ≦ 20 points)
ii) ○: Normal. (Total score <15 points)
iii) △: Bad. (Total score <10 points)
iv) ×; Impossible. (Total score <5 points)
(7) Particle size evaluation method
The particle size was measured with a Coulter Counter N4 (manufactured by Coulter).
The composition of the raw materials used in the following examples, the Tg calculated value of the produced polymer, and the evaluation results of the obtained emulsion compositions are shown in Table 1 for Examples 1 to 10, Examples 11 to 14 and comparison Examples 1 to 4 are shown in Table 2, respectively.
[0100]
Example 1 (weight ratio A layer: B layer = 5: 95)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 5:95, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
[0101]
(1) Reactor
A reactor equipped with a stirrer, a reflux condenser, a dropping device and a thermometer was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
1029.0 parts of pure water
DBS 1.0 part
Snowtex C-30 333.3 parts
(100.0 parts as colloidal silica solid content)
Here, DBS means sodium dodecylbenzenesulfonate, Snowtex C-30 is colloidal silica (product of Nissan Chemical Industries, Ltd.), and colloidal silica solid content conversion is within Snowtex C-30. (The same applies to the following description).
In the reactor, the mixture was heated to 70 ° C. while stirring and mixing in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0102]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
20.0 parts of pure water
DBS 0.125 part
ST 23.0 parts
nBA 17.0 parts
GMA 10.0 parts
(Total monomer 50.0 parts by weight)
Here, ST means styrene, nBA means n-butyl acrylate, and GMA means glycidyl methacrylate (the same applies in the following description).
This monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 1 hour in a reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0103]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer B polymerization.
380.0 parts of pure water
DBS 2.375 parts
MMA 543.0 parts
nBA 382.0 parts
MAc 10.0 parts
AAm 15.0 parts
(Total monomer: 950.0 parts by weight)
Here, MMA means methyl methacrylate, MAc means methacrylic acid, and AAm means acrylamide (the same applies in the following description).
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0104]
(5) Recovery of emulsion composition
The reaction solution in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 40% and an average particle size of 150 nm.
[0105]
Example 2 (weight ratio A layer: B layer = 20: 80)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 20:80, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
In the same manner as in Example 1, a colloidal silica dispersion was prepared.
[0106]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
80.0 parts of pure water
DBS 0.5 part
ST 86.0 parts
nBA 64.0 parts
GMA 50.0 parts
(Total monomer 200.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 2 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0107]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer B polymerization.
320.0 parts of pure water
DBS 2.0 parts
ST 434.0 parts
nBA 321.0 parts
MAc 30.0 parts
AAm 15.0 parts
(Total amount of monomers 800.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0108]
(5) Recovery of emulsion composition
The reaction solution in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 40% and an average particle size of 160 nm.
[0109]
Example 3 (weight ratio A layer: B layer = 30: 70)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 30:70, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
In the same manner as in Example 1, a colloidal silica dispersion was prepared.
[0110]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
120.0 parts of pure water
0.75 parts DBS
ST 111.0 parts
nBA 89.0 parts
GMA 100.0 parts
(Total amount of monomers 300.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 2 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0111]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer B polymerization.
280.0 parts of pure water
DBS 1.75 parts
ST 336.0 parts
nBA 289.0 parts
MAc 60.0 parts
AAm 15.0 parts
(Monomer total 700.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0112]
(5) Recovery of emulsion composition
The reaction solution in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 40% and an average particle size of 160 nm.
[0113]
Example 4 (weight ratio A layer: B layer = 50: 50)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 50:50, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
[0114]
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
3798.7 parts of pure water
DBS 0.5 part
Snowtex C-30 333.3 parts
(100.0 parts as colloidal silica solid content)
In the reactor, the mixture was heated to 70 ° C. while stirring and mixing in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0115]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
200.0 parts of pure water
DBS 1.25 parts
ST 160.0 parts
nBA 140.0 parts
GMA 200.0 parts
(Total monomer: 500.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 3 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0116]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
200.0 parts of pure water
DBS 1.25 parts
ST 139.0 parts
nBA 226.0 parts
MAc 125.0 parts
AAm 10.0 parts
(Total monomer: 500.0 parts by weight)
This B-layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 3 hours in the reactor where the A-layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0117]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 20% and an average particle size of 200 nm.
[0118]
Example 5 (weight ratio A layer: B layer = 50: 50)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 50:50, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
In the same manner as in Example 4, a colloidal silica dispersion was prepared.
[0119]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
200.0 parts of pure water
DBS 1.25 parts
ST 14.0 parts
nBA 86.0 parts
GMA 400.0 parts
(Total monomer: 500.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 3 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0120]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
200.0 parts of pure water
DBS 1.25 parts
ST 139.0 parts
nBA 226.0 parts
MAc 125.0 parts
AAm 10.0 parts
(Total monomer: 500.0 parts by weight)
This B-layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 3 hours in the reactor where the A-layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0121]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 20% and an average particle size of 200 nm.
[0122]
Example 6 (weight ratio A layer: B layer = 20: 80)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 20:80, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
373.0 parts of pure water
DBS 0.5 part
Snowtex C-30 333.3 parts
(100.0 parts as colloidal silica solid content)
In the reactor, the mixture was heated to 70 ° C. with stirring in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0123]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
A monomer emulsion composition for layer A polymerization was prepared in a container separate from the reactor at 70 ° C. while stirring the following in a nitrogen atmosphere.
60.0 parts of pure water
DBS 0.5 part
ST 118.0 parts
nBA 32.0 parts
GMA 50.0 parts
(Total monomer 200.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 3 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0124]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
240.0 parts of pure water
DBS 2.0 parts
ST 558.0 parts
nBA 192.0 parts
MAc 30.0 parts
AAm 20.0 parts
(Total amount of monomers 800.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0125]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 55% and an average particle size of 200 nm.
[0126]
Example 7 (weight ratio A layer: B layer = 20: 80)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 20:80, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
575.2 parts of pure water
DBS 1.0 part
Snowtex C-30 333.3 parts
(100.0 parts as colloidal silica solid content)
In the reactor, the mixture was heated to 70 ° C. with stirring in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0127]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
60.0 parts of pure water
DBS 0.5 part
ST 1.0 part
2EHA 149.0 parts
GMA 50.0 parts
(Total monomer 200.0 parts by weight)
Here, 2EHA means 2-ethylhexyl acrylate (the same applies in the following description).
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 2 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0128]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
240.0 parts of pure water
DBS 2.0 parts
ST 96.0 parts
2EHA 654.0 parts
MAc 30.0 parts
AAm 20.0 parts
(Total amount of monomers 800.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0129]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 50% and an average particle size of 120 nm.
[0130]
Example 8 (weight ratio A layer: B layer = 20: 80)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 20:80, and the weight ratio of the colloidal silica solids to the total organic polymer is 50: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
41.9 parts of pure water
DBS 1.0 part
Snowtex C-30 1666.7 parts
(500.0 parts as colloidal silica solid content)
In the reactor, the mixture was heated to 70 ° C. with stirring in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0131]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
60.0 parts of pure water
DBS 0.5 part
ST 86.0 parts
nBA 64.0 parts
GMA 50.0 parts
(Total monomer 200.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 2 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0132]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
240.0 parts of pure water
DBS 2.0 parts
ST 434.0 parts
nBA 321.0 parts
MAc 30.0 parts
AAm 15.0 parts
(Total amount of monomers 800.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0133]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 50% and an average particle size of 200 nm.
[0134]
Example 9 (weight ratio A layer: B layer = 20: 80)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 20:80, and the weight ratio of the colloidal silica solids to the total organic polymer is 100: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
279.5 parts of pure water
DBS 1.0 part
Snowtex C-30 3333.3 parts
(1000.0 parts as colloidal silica solid content)
In the reactor, the mixture was heated to 70 ° C. with stirring in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0135]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
80.0 parts of pure water
DBS 0.5 part
ST 86.0 parts
nBA 64.0 parts
GMA 50.0 parts
(Total monomer 200.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 2 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0136]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
240.0 parts of pure water
DBS 2.0 parts
ST 434.0 parts
nBA 321.0 parts
MAc 30.0 parts
AAm 15.0 parts
(Total amount of monomers 800.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0137]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 50% and an average particle size of 200 nm.
[0138]
Example 10 (weight ratio A layer: B layer = 50: 50)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 50:50, and the weight ratio of the colloidal silica solids to the total organic polymer is 3: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
564.5 parts of pure water
DBS 2.0 parts
Snowtex C-30 100.0 parts
(30.0 parts in colloidal silica solid content)
In the reactor, the mixture was heated to 70 ° C. with stirring in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0139]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
80.0 parts of pure water
DBS 0.5 part
ST 400.0 parts
nBA 30.0 parts
GMA 70.0 parts
t-DM 0.5 part
(Total monomer: 500.0 parts by weight)
Here, t-DM means t-dodecyl mercaptan (the same applies in the following description).
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 3 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0140]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
200.0 parts of pure water
DBS 1.25 parts
ST 383.0 parts
nBA 55.0 parts
MAc 42.0 parts
MAm 20.0 parts
t-DM 0.5 part
(Total monomer: 500.0 parts by weight)
This B-layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 3 hours in the reactor where the A-layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0141]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 50% and an average particle size of 150 nm.
[0142]
Example 11 (weight ratio A layer: B layer = 90: 10)
The reaction conditions are as follows so that the weight ratio of the organic polymer of the A layer and the B layer is 90:10, and the weight ratio of the colloidal silica solids to the total organic polymer is 30: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
Pure water 1974.2 parts
DBS 102.0 parts
Snowtex C-30 1000.0 parts
(300.0 parts as colloidal silica solid content)
In the reactor, the mixture was heated to 70 ° C. with stirring in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0143]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
360.0 parts of pure water
DBS 2.25 parts
ST 565.0 parts
nBA 285.0 parts
GMA 50.0 parts
(Total monomer 900.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 3 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0144]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
40.0 parts of pure water
DBS 0.25 parts
ST 18.0 parts
nBA 42.0 parts
MAc 30.0 parts
AAm 10.0 parts
t-DM 0.5 part
(Total monomer 100.0 parts by weight)
This B-layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 1 hour in the reactor where the A-layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0145]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 30% and an average particle size of 60 nm.
[0146]
Example 12 (weight ratio A layer: B layer = 20: 80)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 20:80, and the weight ratio of the colloidal silica solids to the total organic polymer is 150: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
758.8 parts of pure water
DBS 1.0 part
Snowtex C-30 5000.0 parts
(1500.0 parts as colloidal silica solid content)
In the reactor, the mixture was heated to 70 ° C. with stirring in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0147]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
80.0 parts of pure water
DBS 0.5 part
ST 86.0 parts
nBA 64.0 parts
GMA 50.0 parts
(Total monomer 200.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 3 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0148]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
320.0 parts of pure water
DBS 2.0 parts
ST 434.0 parts
nBA 321.0 parts
MAc 30.0 parts
AAm 15.0 parts
t-DM 0.5 part
(Total monomer 100.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0149]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 35% and an average particle size of 150 nm.
[0150]
Example 13 (weight ratio A layer: B layer = 95: 5)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 95: 5, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
3632.0 parts of pure water
DBS 0.5 part
Snowtex C-30 333.3 parts
(100.0 parts as colloidal silica solid content)
In the reactor, the mixture was heated to 70 ° C. with stirring in a nitrogen atmosphere, and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a colloidal silica dispersion.
[0151]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
380.0 parts of pure water
DBS 2.375 parts
ST 545.0 parts
nBA 355.0 parts
GMA 50.0 parts
(Total monomer: 950.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 3 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0152]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
20.0 parts of pure water
DBS 0.125 part
nBA 25.0 parts
MAc 25.0 parts
(Total monomer 50.0 parts by weight)
This B-layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 3 hours in the reactor where the A-layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0153]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a non-volatile content of 30% and an average particle size of 220 nm.
[0154]
Example 14 (weight ratio A layer: B layer = 1: 99)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 1:99, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
In the same manner as in Example 1, a colloidal silica dispersion was prepared.
[0155]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
4.0 parts of pure water
DBS 0.02 part
GMA 10.0 parts
(Total monomer 10.0 parts by weight)
This monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 1 hour in a reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0156]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
396.0 parts of pure water
DBS 2.475 parts
ST 559.0 parts
nBA 391.0 parts
MAc 10.0 parts
AAm 20.0 parts
(Total monomer: 980.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0157]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 40% and an average particle size of 150 nm.
[0158]
Comparative Example 1 (weight ratio A layer: B layer = 5: 95)
An emulsion composition containing no colloidal silica in the A layer or in the particles was prepared so that the weight ratio of the organic polymer in the A layer and the B layer was 5:95.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of dispersion without colloidal silica
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
112.8 parts of pure water
DBS 1.0 part
In the reactor, while stirring and mixing the above mixture in a nitrogen atmosphere, the temperature was raised to 70 ° C. and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a dispersion containing no colloidal silica. did.
[0159]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
20.0 parts of pure water
DBS 0.125 part
ST 23.0 parts
nBA 17.0 parts
GMA 10.0 parts
(Total monomer 50.0 parts by weight)
The monomer A emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 1 hour in a reactor charged with the above dispersion containing no colloidal silica to carry out a polymerization reaction. . After completion of the dropwise addition, aging was further performed for 2 hours.
[0160]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
380.0 parts of pure water
DBS 2.375 parts
MMA 543.0 parts
nBA 382.0 parts
MAc 10.0 parts
AAm 15.0 parts
(Total monomer: 950.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0161]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 40% and an average particle size of 150 nm.
[0162]
Comparative Example 2 (weight ratio A layer: B layer = 50: 50)
An emulsion composition containing no colloidal silica in the A layer or in the particles was prepared so that the weight ratio of the organic polymer in the A layer and the B layer was 50:50.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of dispersion without colloidal silica
The reactor was charged with the following and mixed with stirring under a nitrogen atmosphere.
3632.0 parts of pure water
DBS 0.5 part
In the reactor, while stirring and mixing the above mixture in a nitrogen atmosphere, the temperature was raised to 70 ° C. and maintained at this temperature, and 5.0 parts of ammonium persulfate was added to prepare a dispersion containing no colloidal silica. did.
[0163]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
200.0 parts of pure water
DBS 1.25 parts
ST 160.0 parts
nBA 140.0 parts
GMA 200.0 parts
(Total monomer: 500.0 parts by weight)
Into a reactor charged with the above dispersion containing no colloidal silica, the monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 3 hours to carry out a polymerization reaction. . After completion of the dropwise addition, aging was further performed for 2 hours.
[0164]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
200.0 parts of pure water
DBS 1.25 parts
ST 139.0 parts
nBA 226.0 parts
MAc 125.0 parts
AAm 10.0 parts
(Total monomer: 500.0 parts by weight)
This B-layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 3 hours in the reactor where the A-layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0165]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 20% and an average particle size of 200 nm.
[0166]
Comparative Example 3 (weight ratio A layer: B layer = 20: 80)
The reaction conditions are as follows so that the weight ratio of the organic polymer in the A layer and the B layer is 20:80, and the weight ratio of the colloidal silica solids to the total organic polymer is 10: 100. To prepare an emulsion composition.
(1) Reactor
The same reactor as in Example 1 was used.
(2) Preparation of colloidal silica dispersion
In the same manner as in Example 1, a colloidal silica dispersion was prepared.
[0167]
(3) Polymerization of layer A (core)
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. in a nitrogen atmosphere to prepare a monomer emulsion composition for layer A polymerization.
80.0 parts of pure water
DBS 0.5 part
ST 122.0 parts
nBA 78.0 parts
(Total monomer 200.0 parts by weight)
The monomer emulsion composition for layer A polymerization was continuously dropped into the reaction solution over 2 hours into the reactor in which the colloidal silica dispersion was charged, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0168]
(4) B layer (shell) polymerization
In a container separate from the reactor, the following were stirred and mixed at 70 ° C. under a nitrogen atmosphere to prepare a monomer emulsion composition for B layer polymerization.
320.0 parts of pure water
DBS 2.0 parts
ST 434.0 parts
nBA 321.0 parts
MAc 30.0 parts
AAm 15.0 parts
(Total amount of monomers 800.0 parts by weight)
This B layer polymerization monomer emulsion composition was continuously dropped into the reaction solution over 4 hours in the reactor where the A layer polymerization reaction was completed, and a polymerization reaction was performed. After completion of the dropwise addition, aging was further performed for 2 hours.
[0169]
(5) Recovery of emulsion composition
The reaction liquid in the reactor after completion of the B layer polymerization reaction was cooled to room temperature, adjusted to pH 8.0 with aqueous ammonia, and recovered as an emulsion composition.
The emulsion composition contained particles having a nonvolatile content of 40% and an average particle size of 160 nm.
[0170]
Comparative Example 4 (weight ratio A layer: B layer = 5: 95)
The emulsion (weight ratio A layer: B layer = 5: 95) obtained in Comparative Example 1 and Snowtex C-30 were mixed at the following ratio.
Emulsion (Comparative Example 1) 1000.0 parts
Snowtex C-30 133.3 parts
(40.0 parts in terms of colloidal silica solid content)
[0171]
[Table-1]

[0172]
[Table-2]

[0173]
【The invention's effect】
As is clear from the comparison of the evaluation results of Examples and Comparative Examples shown in Tables 1 and 2, the emulsion composition according to the present invention relates to various properties of the coating (coated film, film, etc.) obtained from the emulsion composition. In the case of a thing, it has the outstanding water resistance, solvent resistance, adhesiveness, and blocking resistance compared with the case of the emulsion composition by a prior art.
The water-based dispersible coating composition according to the present invention has at least the following characteristics (1) to (4).
[0174]
(1) Silica is not covalently bonded to organic polymer, but physicochemical and / or secondary bond (hydrogen bond, hydrophobic bond, van der Waals bond, etc.) in the particle by the network structure of organic polymer. Since it is held, there is no functional group having reactivity with silica that causes gelation in the organic polymer, and therefore, the storage stability of the particles or the particle-containing composition is excellent.
(2) Since the composition is a one-pack type (one-component system that does not require a mixing operation just before use) having excellent storage stability, a two-pack type (for example, a resin component and a curing agent component are used just before use). Compared with the two-component system to be mixed), the pot life is long and the operability is good.
(3) Since the core / shell particles contained in the composition form a three-dimensional cross-linking structure at the time of coating film formation or film formation, the core / shell particles are obtained when the film is formed at MFT (minimum film forming temperature) or higher. Excellent durability (solvent resistance, heat resistance, adhesion to ground, water resistance), excellent physical properties (elasticity, elongation properties, toughness), excellent appearance properties (smoothness, sharpness) Etc.).
(4) The core / shell particles contained in the composition have silica in the core, and physicochemical and / or secondary bonds (hydrogen bonds, It has excellent blocking resistance because it is retained in the particles by hydrophobic bonds, van der Waals bonds, etc.
[0175]
Therefore, the emulsion composition according to the present invention comprises a paint, a coating agent, an opaque agent, an adhesive, printing ink, paper processing, thermal paper / pressure-sensitive paper processing, fiber processing, thickener for textiles, pigment dispersant, cosmetics. It can be suitably used in a wide range of fields such as blends and cement admixtures.

Claims (10)

 It has a core / shell particle structure, a core monomer (c1) having an epoxy group and an unsaturated double bond in the molecule, and a functional group reactive with the epoxy group and an alkoxysilane group. At least one monomer selected from the group consisting of monoethylenically unsaturated monomers not present in the core, as a core monomer (c2), having an unsaturated double bond in the molecule, and At least one monomer selected from the group consisting of a monoethylenically unsaturated monomer having no functional group reactive with an epoxy group, an epoxy group and an alkoxysilane group in the molecule, and a core A core (C) obtained by polymerization in a reaction system containing at least one type of colloidal silica as colloidal silica (c3), an unsaturated double bond and an epoxy group as shell monomer (s1) Reactive with At least one monomer selected from the group consisting of monoethylenically unsaturated monomers having a functional group in the molecule and having no epoxy group or alkoxysilane group in the molecule; and a shell Monoethylenic unsaturation as the monomer (s2), which has an unsaturated double bond in the molecule and does not have a functional group reactive with an epoxy group, an epoxy group or an alkoxysilane group in the molecule Particles having a shell (S) obtained by polymerization in a reaction system containing at least one monomer selected from the group consisting of monomers.   It has a core / shell particle structure, the core monomer (c1) has an unsaturated double bond and a functional group reactive with an epoxy group in the molecule, and an epoxy group and an alkoxysilane group are molecules. As an at least one monomer selected from the group consisting of monoethylenically unsaturated monomers not present in the core, and as a core monomer (c2), it has an unsaturated double bond in the molecule. And at least one monomer selected from the group consisting of monoethylenically unsaturated monomers having no functional groups reactive with epoxy groups, epoxy groups and alkoxysilane groups in the molecule, core A core (C) obtained by polymerization in a reaction system containing at least one type of colloidal silica as colloidal silica (c3), and an epoxy group and an unsaturated double bond as shell monomer (s1) In the molecule And at least one monomer selected from the group consisting of a monoethylenically unsaturated monomer having no functional group reactive with an epoxy group and an alkoxysilane group in the molecule, and a shell unit As the monomer (s2), a monoethylenically unsaturated monomer having an unsaturated double bond in the molecule and having no functional group reactive with the epoxy group, epoxy group or alkoxysilane group in the molecule. Particles having a shell (S) obtained by polymerization in a reaction system containing at least one monomer selected from the group consisting of monomers.  Monoethylenically unsaturated monomer having an unsaturated double bond in the molecule used for polymerizing the core (C), and unsaturated double bond used in polymerizing the shell (S) in the molecule The core / colloidal silica (c3) is 1 to 100 parts by weight with respect to a total weight of 100 parts by weight of the monoethylenically unsaturated monomer that is contained. Particles.  Monoethylenically unsaturated monomer having an unsaturated double bond in the molecule used for polymerizing the core (C) and an unsaturated double bond used in polymerizing the shell (S) in the molecule 3. The particle according to claim 1, wherein the weight ratio of the monoethylenically unsaturated monomer is 5:95 to 90:10. 4.  The particle according to any one of claims 1 to 4, wherein the core colloidal silica (c3) is a water dispersion type.  An aqueous dispersible composition having the characteristics of an emulsion, latex, or suspension, comprising the particles according to claim 1 as a dispersed phase and water as a continuous phase.  An aqueous dispersible coating composition comprising the aqueous dispersible composition according to claim 6.  As step 1 (core particle formation step), in the aqueous continuous phase containing a radical polymerization initiator, the core monomer (c1) has an epoxy group and an unsaturated double bond in the molecule, and the epoxy group As a core monomer (c2), at least one monomer selected from the group consisting of a monoethylenically unsaturated monomer that does not have a functional group and an alkoxysilane group reactive in the molecule, Selected from the group consisting of monoethylenically unsaturated monomers having unsaturated double bonds in the molecule and no functional groups reactive with epoxy groups, epoxy groups and alkoxysilane groups in the molecule The reaction system containing at least one kind of monomer and at least one kind of colloidal silica as the core colloidal silica (c3) is subjected to emulsion polymerization or suspension polymerization at a temperature of 10 ° C to 100 ° C In the aqueous continuous phase containing the radical polymerization initiator in which the core polymer obtained in step 1 (core particle forming step) is dispersed as step 2 (shell forming step) As the shell monomer (s1), a monoethylenic compound having an unsaturated double bond and a functional group reactive with an epoxy group in the molecule, and no epoxy group or alkoxysilane group in the molecule As an at least one monomer selected from the group consisting of unsaturated monomers and a shell monomer (s2), it has an unsaturated double bond in the molecule and is reactive with an epoxy group A reaction system containing at least one monomer selected from the group consisting of a monoethylenically unsaturated monomer having no functional group, epoxy group and alkoxysilane group in the molecule at a temperature of 10 ° C. 1 And a step of forming core / shell particles by performing emulsion polymerization or suspension polymerization at 0 ° C., and steps 1 and 2 are related by continuous emulsion polymerization or suspension polymerization. And the relative amount of the core-forming monomer and the shell-forming monomer is such that the ratio of the core polymer weight to the shell polymer weight in the resulting particles is from 5:95 to 90:10. A method for producing an aqueous dispersion having the characteristics of an emulsion, latex or suspension, comprising water-insoluble core / shell polymer particles as a dispersed phase and water as a continuous phase.  In step 1 (core particle formation step), in the aqueous continuous phase containing a radical polymerization initiator, as the core monomer (c1), a functional group reactive with an unsaturated double bond and an epoxy group is introduced in the molecule. And at least one monomer selected from the group consisting of monoethylenically unsaturated monomers having no epoxy group and alkoxysilane group in the molecule, as a core monomer (c2), Selected from the group consisting of monoethylenically unsaturated monomers having unsaturated double bonds in the molecule and no functional groups reactive with epoxy groups, epoxy groups and alkoxysilane groups in the molecule The reaction system containing at least one kind of monomer and at least one kind of colloidal silica as the core colloidal silica (c3) is subjected to emulsion polymerization or suspension polymerization at a temperature of 10 ° C to 100 ° C. In the aqueous continuous phase containing the radical polymerization initiator in which the core polymer obtained in step 1 (core particle forming step) is dispersed as step 2 (shell forming step) As the shell monomer (s1), a monoethylenic compound having an epoxy group and an unsaturated double bond in the molecule, and a functional group reactive with the epoxy group and an alkoxysilane group in the molecule As an at least one monomer selected from the group consisting of unsaturated monomers and a shell monomer (s2), it has an unsaturated double bond in the molecule and is reactive with an epoxy group A reaction system containing at least one monomer selected from the group consisting of a monoethylenically unsaturated monomer having no functional group, epoxy group and alkoxysilane group in the molecule at a temperature of 10 ° C. 1 And a step of forming core / shell particles by performing emulsion polymerization or suspension polymerization at 0 ° C., and steps 1 and 2 are related by continuous emulsion polymerization or suspension polymerization. And the relative amount of the core-forming monomer and the shell-forming monomer is such that the ratio of the core polymer weight to the shell polymer weight in the resulting particles is from 5:95 to 90:10. A method for producing an aqueous dispersion having the characteristics of an emulsion, latex or suspension, comprising water-insoluble core / shell polymer particles as a dispersed phase and water as a continuous phase.  An aqueous dispersion produced by the production method according to claim 8 or 9.