JPS6356543A - Alkoxy titanium based surface-treating agent - Google Patents

Abstract

PURPOSE:To obtain the titled surface-treating agent suitable to resin-filler composite system and having excellent effect to improvement of physical properties of moldings, by reacting a tetraalkoxytitanium and/or condensation polymer thereof with itaconic anhydride or itaconic half ester. CONSTITUTION:A tetraalkoxytitanium (e.g. tetraisopropoxytitanium) and/or hydrolyzed condensation polymer thereof having <=6 average condensation degree is reacted with itaconic anhydride or itaconic half ester to provide the aimed alkoxytitanium derivative wherein 35-90% free substituting group is RO group (R is 1-6C alkyl having straight chain or side chain) and the remainder is a group expressed by the formula (R' and R is 1-6C alkyl having straight chain or side chain).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an alkoxytitanium-based surface treatment agent, and more particularly, a part of the free substituents of tetraalkoxytitanium or its polymer is replaced with itaconic acid hafester residue. The present invention relates to a surface treatment agent containing an alkoxytitanium derivative substituted with a group as an active ingredient.

The surface treatment agent of the present invention improves the dispersibility and processability of the filler in the polymer when producing a composite of a solid substance and a polymer, for example, a composite in which a filler is dispersed in the polymer. In order to improve the physical properties of the resulting composite, the surface of the filler is treated or the filler is used by being added and mixed with a polymeric medium. In particular, it is suitable as a surface treatment agent for forming a photocurable filler-polymer composite coating film.

[Conventional technology]

It has been well known that when producing a composite of a solid material and a polymeric material, the properties of the composite can be improved by surface treating the solid material using an organic titanium compound. For example, aliphatic or aromatic carboxylic acid residues or JP-A-54-81353 discloses that the use of an alkoxytitanium derivative with an itaconic acid Hafester residue added thereto as a surface treatment agent improves the dispersibility and processability of fillers into polymeric substances. has been done.

In addition, a surface treatment agent containing as an active ingredient an alkoxytitanium derivative having a photopolymerizable (meth)acryloyl group in the molecule, synthesized by reacting tetraalkoxytitanium with acrylic acid or methacrylic acid, has been published in U.S. Patent No. 4,
No. 094,853.

However, the alkoxy titanium and/or
or a surface treatment agent whose active ingredient is an alkoxytitanium derivative in which only itaconic acid hafester residues are introduced into some of the free substituents of the hydrolyzed condensation product, and a filler-polymer material composite using this surface treatment agent. There are no known documents describing the physical properties of molded bodies of this system.

[Problem that the invention seeks to solve]

The alkoxytitanium F-1 body disclosed in the cited Japanese Patent Application Laid-open No. 54-81353 has been recognized to be effective in improving the dispersibility of fillers into polymeric substances and the processability of filler-polymeric substance composite systems. However, good results are not necessarily obtained with respect to the mechanical properties and electrical properties of the resulting filler-polymer composite molded product, except for certain composite systems.
On the contrary, it may decrease. In particular, in a photocuring system in which a polymeric substance is cured by irradiation with light, the photocurability of the polymeric substance is inhibited, making it impossible to obtain a good cured product.

On the other hand, the alkoxytitanium derivatives described in US Pat. No. 4,094,853 are extremely unstable and polymerize and gel during storage, making them impractical.

An object of the present invention is to provide a surface treatment agent that is effective in a filler-photocurable resin system and has an excellent effect on improving the physical properties of a filler-polymer composite molded article. .

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors have discovered that an alkoxytitanium derivative synthesized from tetraalkoxytitanium and/or its condensation polymer and itaconic anhydride or itaconic acid hafester can be used as a filler and as a polymer. The present invention was completed based on the discovery that the present invention exhibits excellent effects as an active ingredient of a surface treatment agent in a composite system with a substance.

The present invention relates to a reaction product of a hydrolyzed condensation product (polymer) of tetraalkoxytitanium and/or tetraalkoxytitanium having an average degree of condensation of 6 or less and itaconic anhydride or itanoic acid half ester, which is free-substituted base 3
5 to 90% are RO- groups (wherein R is an alkyl group having 1 to 6 carbon atoms having a straight chain or a side chain (herein, R'' is a carbon number having the same or different straight chain or side chain as R) This is an alkoxytitanium-based surface treatment agent characterized by containing an alkoxytitanium derivative (representing an alkyl group of 1 to 6).

The surface treatment agent of the present invention has the following general formula (1): (where,
R and P' represent the same meanings as above, and n is 1 or 2. ) has one bond of -T'i -0-T' in 5 molecules of the alkoxy titanium derivative/monomer represented by
The active ingredient is a oxytitanium FA' tetramer, a polymer, or a mixture of these monomers and a polymer.

R and R in the substituents include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
Examples include alkyl groups having 1 to 6 carbon atoms having a straight chain or a side chain such as a tert-7'' tyl group, a pentyl group, and an n-hexyl group, and all of these may be the same substituent, and
Different substituents may be used.

The surface treatment agent of the present invention has the general formula: (RO)4Ti
(Here, R represents the same meaning as above.) It can be synthesized by reacting 1 to 2 moles of itaconic anhydride or itaconic acid hafester with 1 mole of tetraalkoxytitanium represented by the formula (R represents the same meaning as above).

The reaction between tetraalkoxytitanium and itaconic anhydride is
In the following reaction formula (3), the reaction between tetraalkoxytitanium and itaconic acid hafester is shown in the following reaction formula (4).
It is expressed as

(RO) 4Ti + n C3H4CzOs =
・(RO)(4-fl+Ti(OOC-CJ4COO
R) −−・−(3) (RO), Ti + n1loOc
-Cd5-COOR' --(RO)u-+nTi(O
OC-CsHa C0OR')*+nROH--
・(41 (herein, R and R′ represent the same meanings as above, and n is 1 or 2.) In addition, in these reactions, dialkyl esterification of itaconic anhydride or itaconic acid hafester is carried out. This occurs as a side reaction, and alkoxy titanium is hydrolyzed and polycondensed by the water produced in this esterification reaction, and some of the alkoxy titanium derivatives/polymers are produced as by-products.Therefore, in these reactions, reaction formula (3) or (4
) can be obtained under normal reaction conditions and used as a surface treatment agent without separating by-products. Alternatively, the monomer and polymer may be separated by extraction or the like, and each may be used as a surface treatment agent.

In addition, the molar ratio of the tetraalkoxytitanium to the total number of free substituents of the alkoxytitanium polymer having an average degree of condensation of 6 or less that has been previously hydrolyzed and polycondensed is 0.1.
~0.65% of the free RO- groups of the alkoxytitanium polymer are replaced with phthalic acid hafester residues by reacting itaconic anhydride or itaconic acid hafestel with an average degree of condensation of 6 or less. Surface treatment agents containing alkoxy titanium derivatives/polymers as main components can be produced.

In these reactions, as the starting material tetraalkoxytitanium, tetraisopropoxytitanium and tetra-n-butoxytitanium are preferably used from the viewpoint of hydrolyzability of the surface treatment agent, ease of availability, and the like. On the other hand, itaconic acid hafestel can be synthesized by equimolar reaction of itaconic anhydride and alcohol. In the above reaction, there is no particular need to use pure itaconic acid hafestel, and the reaction solution obtained by this reaction is You may use it as is. In addition, as itaconic acid hafestel,
Hafester with isopropanol or normal butanol is preferably used.

The reaction of the tetraalkoxytane monomer and/or tetraalkoxytane polymer with itaconic anhydride or itaconic acid hafestel is carried out under stirring at a temperature of 40 to 80° C. for 2 to 6 hours in the presence or absence of a solvent. I will do it. Further, the hafestation reaction of itaconic anhydride is carried out by stirring and maintaining at a temperature of 40 to 80° C. for 2 to 6 hours in the presence or absence of a solvent.

The surface treatment agent of the present invention can be blended into a wide range of mixed systems of polymeric media and fillers, and used to reduce the viscosity of the mixed system, improve the dispersibility of fillers, and improve the physical properties of cured products. be done. These may be used alone (or may be used dissolved in a solvent, or may be used in combination with other surface treating agents or solvents).

Examples of polymeric media include polyethylene, polypropylene, polyvinyl chloride, polyester, polycarbonate, alkyd resin, acrylic resin, polyvinylidene fluoride, polyamide, polysulfone, polysulfide, polyphenylene oxide, xylene resin, nitrocellulose, chlorinated rubber, Examples include chlorinated polyethylene, polystyrene, styrene-butadiene copolymer, polyacrylonitrile, and the like.

On the other hand, as fillers, relatively inert solids are added to polymeric materials for the purpose of reducing the unit cost of the polymeric material, improving processability and physical properties, imparting color effects, etc. For example, calcium carbonate, kaolin, clay,
Mica, talc, calcium silicate, titanium oxide, iron oxide, silica, carbon black, calcium sulfate, barium sulfate, aluminum powder, zinc powder, glass fiber,
Examples include wood flour, paper and fiber powders, synthetic and natural powders, pigments and extender pigments used in the paint industry.

The surface treatment agent of the present invention can be added to the polymer medium in advance and mixed (method of adding it at the same time when mixing the filler to the polymer medium, or coating the surface of the filler in advance, etc.). It may be used in any method.The amount used as a surface treatment agent is 0.1 to 5 parts by weight, preferably 0.2 to 1 part by weight, per 100 parts by weight of the filler.Amount used If it is too small, the effect of its use will be small, and even if it is used in excess, the expected effect will not increase.

[For production]

As described above, the surface treatment agent of the present invention has 1 to 2 relatively short-chain itaconic acid hafester residues as free substituents.
It is characterized by containing an alkoxytitanium derivative as an active ingredient. The alkoxy group (RO- group) is a hydrolyzable reactive group, and R is preferably an alkyl group having 1 to 6 carbon atoms. When the number of carbon atoms in R becomes large, the alkoxy titanium derivative and the filler This is not preferable because the reactivity with adhering moisture and 110-groups present on the surface decreases.

On the other hand, itaconic acid hafester residue (00CC3) 1
4COOR' group) is a lipophilic group (visual lipophilic group) having an unsaturated double bond and an ester bond in its structure,
is preferably an alkyl group having 1 to 6 carbon atoms, and R
If the number of carbon atoms in o becomes large, this is not preferable because it causes selectivity in the resin, which is a polymeric medium. More preferably, the number of carbon atoms in R'' is 3 or 4. Furthermore, the average degree of condensation of the alkoxy titanium derivative is preferably 6 or less, and if the average degree of condensation is too large, the molecule as a surface treatment agent becomes too large. , it becomes difficult to effectively adhere to the surface of the filler, so the surface treatment effect decreases.Furthermore, the content of alkoxy groups in the free substituents of the alkoxy titanium derivative is 35 to 9.
The content is preferably 0%; if the alkoxy group content is too low, the reactivity with the filler will decrease, and if it is too high,
The amount of itaconic acid Hafester residue becomes too small and the appearance of lipophilicity decreases.

By specifying the structure of the alkoxy titanium derivative as its active ingredient as described above, the surface treatment agent of the present invention can be applied to thermoplastic resins such as polyethylene, polypropylene, polystyrene, ethylene/propylene rubber (E
PDM), acrylic rubber, Alfin rubber, etc., the double bond in the itaconic acid hafester residue opens and bonds to the resin main chain during heat molding, and the resin and filler are crosslinked.
The mechanical and electrical properties of the composite after molding are improved. In particular, in the case of a surface treatment agent whose main component is an alkoxytitanium monomer having 1 to 2 itaconic acid Hafester residues per 1 Ti atom, the effect of improving properties is large.

On the other hand, thermosetting resins such as unsaturated polyester resins, polybutadiene resins, rubber [(BR, SBR, NB
In the case of resins having unsaturated groups such as R, IR, IIR, natural rubber, etc., when cured by heating or irradiation with active energy rays, such as ultraviolet rays, electron beams, radiation, etc., itaconic acid hafester residues themselves also It polymerizes, improving the crosslinking density of the resin system, further improving the bonding properties between the filler and the resin, and improving the properties of the composite system.

As a result, compared to conventional alkoxy titanium-based surface treatment agents, it has extremely superior viscosity reduction properties in composite polymer systems consisting of polymer substances and fillers, such as paints, inks, composite molded objects, etc. effect, filler dispersion effect, physical property improvement effect of cured product, etc.

〔Example〕

The present invention will be explained in more detail with reference to Examples and Comparative Examples.

However, the scope of the present invention is not limited in any way by the following examples.

Note that "parts" and "%" in the following sections are based on weight unless otherwise specified.

(1) Synthesis of alkoxytitanium derivative (al sample (T-1) 1 mol (2
84 parts) and 1 mole of itaconic anhydride (1
12 parts) was gradually added, heated to 65°C, and kept under stirring for 3 hours until the color became pale yellow and transparent, and the viscosity at 25°C was 3.
Sample (T-1) 396 8 poise viscous liquid
I got the department.

The obtained sample (T-1) was subjected to an infrared absorption spectrum (IR
), absorption based on unsaturated double bonds and ester bonds was observed, and ignition residue (TiO
□) As a result of quantitative analysis using the method, the Ti content was 12°1%.
Met.

From the above analysis results, it is estimated that sample (T-1) is mainly composed of an alkoxytitanium derivative monomer in which one of the isopropoxy groups of tetraisopropoxytitanium is replaced with an itaconic acid monoisopropyl ester residue. did.

(b) Sample (T-2) Sample (T-1) was synthesized under the same conditions as the synthesis of (T-1) except that the amount of itaconic anhydride used was changed to 2 mol (224 parts). The reaction was carried out, and the Ti content was 9.4%.
A sample whose main component is an alkoxytitanium derivative monomer presumed to have two isopropoxy groups of tetraisopropoxytitanium with a viscosity of 7.4 poise at 25°C replaced with phthalic acid mono-n-butyl ester residues. (T-2) was obtained.

(C) Sample (T-3) Into the same reaction apparatus as that used in the synthesis of sample (T-1), 830 parts (1 930 parts of an equimolar reaction product of itaconic anhydride and n-butanol (equivalent to 5 moles as itaconic acid mono-n-butyl ester) was gradually added, heated to 70°C, and kept under stirring for 3 hours. Thereafter, the by-product isopropanol was distilled off under reduced pressure to obtain 1460 parts of sample (T-3), which was a pale yellow transparent viscous liquid having a viscosity of 2800 poise at 25°C.

As a result of IR analysis of the obtained sample (T-3), absorption based on unsaturated double bonds and ester bonds was observed, and as a result of quantitative analysis using the ignition residue (TiO□) method, T
The i content was 13.1%.

From the above analysis results, sample (T-3) is a polymer whose main component is an alkoxytitanium derivative in which some of the free substituents of the isopropoxytitanium polymer have been replaced with itaconic acid mono-n-butyl ester residues. estimated that.

(d) Comparative sample (CT-1) In the synthesis of sample (T-1), 2 mol (564 parts) of oleic acid was added in place of 1 mol of itaconic anhydride and stirred. Although there was some heat generation, the mixture was gradually heated and maintained at 100° C. with stirring for 1 hour, and then the by-produced isopropanol was distilled off under reduced pressure. 1 mol (112 parts) of itaconic anhydride was added to the obtained reaction product, and the mixture was stirred and maintained at 120°C for 1 hour.
A pale yellow color whose main component is an alkoxytitanium derivative monomer that is presumed to have one isopropoxy group, one itaconic acid monoisopropyl ether residue, and two oleic acid residues bonded to one i atom. A comparative sample (CT-1) was obtained which was transparent and had a viscosity of 8.3 poise at 25°C.

(d), comparative sample (CT-2) In the synthesis of comparative sample (CT-1), oleic acid 2
The reaction was carried out under the same conditions as the synthesis of the comparative sample (CT-1) except that 2 moles (564 parts) of isostearic acid was used instead of 1 mole of isostearic acid. A comparative sample (C
T-2) was obtained.

(e) Comparative sample (CT-3) In the synthesis of comparative sample (CT-1), 1 mol (284 parts) of isostearic acid was used in place of 2 mol oleic acid, and 1 mol (284 parts) of itaconic anhydride was used. The reaction was carried out under the same conditions as for the synthesis of the comparative sample (CT-1) except that the molar ratio was changed, and for one Ti atom, one isopropoxy group, two itaconic acid monoisopropyl ether residues and isostearic acid 25 whose main component is an alkoxytitanium derivative monomer presumed to have one residue bonded to it.
A comparative sample (CT-3) with a viscosity of 6.7 voids at
) obtained the division.

(f) Comparative sample (CT-4) In the synthesis of sample (T-1), 3 moles (258 parts) of methacrylic acid was gradually added in place of 1 mole of itaconic anhydride while stirring. There is some heat generation, but it gradually heats up to 60℃.
After stirring and holding for 2 hours, the by-produced isopropanol was distilled off under reduced pressure, and it is estimated that one isopropoxy group and three methacrylic acid residues were bonded to one Ti atom. A comparative sample (cT-4) was obtained, which was composed mainly of an alkoxytitanium derivative monomer and had a transparent pale yellow color and a viscosity of 4.5 poise at 25°C.

The comparative sample (CT-4) gelled after being stored at a temperature of 25° C. for 3 days.

(g) Comparative sample (CT-5) In the synthesis of comparative sample (CT-4), except for using 2 moles (344 parts) of mono-n-butyl maleate after chemical modification to 3 moles of methacrylic acid, (CT-4) The reaction was carried out under the same conditions as in the synthesis of 4), and a seven-piece alkoxy titanium derivative was obtained, which is estimated to have two isopropoxy groups and two maleic acid mono-n-butyl ester residues bonded to one Ti atom. A comparative sample (CT-5) containing - as a main component and having a viscosity of 7.1 poise at 25°C was obtained.

Table 1 shows the specifications of the samples synthesized above and comparative samples.

(The following is a blank space) (2) Dioctyl phthalate - 200 parts of calcium carbonate-based dioctyl phthalate was added with the alkoxy titanium derivatives (T-1) to (T-3) and (CT-1) to (CT-1) synthesized in Section 11 above. Dissolve 3 parts of each of 5), add 300 parts of calcium carbonate (manufactured by Shiraishi Kogyo ■, trade name: Whiten 5SB), and use a ball mill to dissolve 20 parts of each.
Kneaded for hours.

The viscosity of the obtained kneaded product at 25°C was measured using a rotational viscometer (
Measurements were made using a Tokyo Keiki Co., Ltd.).

For comparison, the viscosity of a system without the addition of an alkoxytitanium derivative was also measured.

The results of the viscosity measurements are shown in Table 1.

(3) Unsaturated polyester-calcium carbonate system +1 above
Alkoxytitanium derivatives (T-1) synthesized in Section 1 ~ (
T-3) and (CT-1) to (CT-5) and heavy calcium carbonate (manufactured by Shiroishi Industries, product name: Whiten SB)
) and an orthophthalic acid-based unsaturated polyester resin for -1'IQ lamination were kneaded for 30 minutes using an Ishikawa miller.

To 100 parts of the obtained unsaturated polyester-calcium carbonate composition, 1 part of t-butyl perbenzoate, 7 parts of lead stearate, 1 part of magnesium hydroxide, and 15 parts of 1/4" chopped grass were blended, and mixed using a kneader. Kneaded.

The obtained kneaded material was heated at a pressure of 20 kg/CrA and a temperature of 180 kg/CrA.
Compression molding was performed under molding conditions of °C to obtain test pieces for measuring physical properties.

Using the obtained test piece, various physical properties were measured in accordance with JIS-6911.

For comparison, a system using heavy calcium carbonate that had not been surface-treated with an alkoxytitanium derivative was also subjected to the same treatment and its physical properties were measured.

The measurement results are shown in Table 2.

(Left below) (4) Polypropylene-calcium carbonate system In advance, the alkoxytitanium derivative (T-1) synthesized in the above (1)
) ~ (T-3) and (CT-1) ~ (CT-3) surface-treated calcium carbonate (Shiraishi Kogyo (!)
After kneading 100 parts of Kiku (product name: Whiten 5SB) and 40 parts of polypropylene (manufactured by Ube Industries ■, J-605H) at a temperature of 185 to 190°C using two rolls,
Cooled and ground.

The obtained pulverized product was heated at 200°C x 500k using a heat press.
A test piece was obtained by molding under the conditions of g/crA.

The melt viscosity of the pulverized product and the mechanical properties of the test piece were measured.

These measurement results are shown in Table 3 together with a comparative example of a system using calcium carbonate that has not been surface-treated with an alkoxytitanium derivative.

(Left below) (5) Polybutadiene-talley based UV curing paint At least 65% of the butadiene units in the polymer chain are 1,2-unsaturated bonds, with a number average molecular weight of 1.450 and a hydroxyl value of 65.8, at the molecular end. Polybutadiene with hydroxyl group (manufactured by Nippon Soda, trade name: Nl5SO-PBG-1000)
and 2.4-) N reacted with lylene diisocyanate
Urethane-modified polybutadiene with a GO content of 2.01% and bisphenol A type diglycidyl ether with an epoxy content of 1450 (manufactured by Shell Chemical ■, trade name, Epicoat 10)
01) to react with epoxy and 1700% urethane.
Epoxy-modified polybutadiene was synthesized. The obtained urethane-epoxy modified polybutadiene and propylene glycol dimethacrylate are reacted to produce a methacrylic-urethane-epoxy modified polybutadiene having a methacryloyl group at the end of a pale yellow transparent viscosity of 65 centipoise (20°C, Brookfield type rotational viscometer). was synthesized.

The synthesized modified polybutadiene and the fired resin which had been surface-treated in advance with the alkoxy titanium derivatives (T-1) to (T-3) and (CT-1) to (CT-5) synthesized in Section 11 were combined. A paint was prepared by mixing using a three-roll paint-forming device.For comparison, a paint was prepared using a baked paint that had not been surface-treated with an alkoxytitanium derivative.

5 parts by weight of benzoin methyl ether as a photopolymerization initiator was added and mixed to 100 parts by weight of each of the prepared paints, and the mixture was coated on a tin plate to a thickness of 10 to 50 μm.
Output of 120W/cm using Kw high pressure mercury lamp,
It was irradiated with light and cured at a line speed of 10 m/min.

The properties of the cured coating film are shown in Table 4 along with the coating composition.

(Left below) (6) Acrylic copolymer - titanium white thread paint Copolymerized methyl acrylate, ethyl acrylate, methyl methacrylate and N,N''-dimethylaminoethyl methacrylate, number average molecule i!73,000, glass A mixed solvent solution containing 33.5% by weight of a copolymer with a transition point of 5 °C, trimethylolpropane trimethacrylate, and the alkoxytitanium derivative (T
-1) to (T-3) and (CT-1) to (CT-3)
Titanium white, which had been surface-treated in advance, was mixed into a paint using a three-roll paint-forming device. For comparison, a paint was prepared using titanium white that had not been surface-treated with an alkoxytitanium derivative.

Each of the resulting paints was coated with two coats of epoxy primer.
0.6m with a coating film coated to a thickness of μm and cured by heat.
The thinner was applied onto an electrogalvanized steel sheet with a thickness of m using a bar coater and placed in a hot air oven at 130° C. for 3 minutes to volatilize the thinner.

Then, using an ICT electron beam accelerator with a voltage of 300 KV and a current of 65 mA, an electron beam of 2 Mrad was irradiated in a nitrogen atmosphere to cure the coating film.

The properties of the cured coating film are shown in Table 5 along with the coating composition.

(The following is a blank space) [Effects of the Invention] From the results of the examples shown in Tables 1 to 5 above, it is clear that the surface treatment agent of the present invention contains an alkoxytitanium derivative having only an itaconic acid Hafester residue in addition to the alkoxy group as an active ingredient. are surface treatment agents (sample numbers CT-1 to
Compared to CT-3), by adding it to the resin-inorganic filler composite system or using it for pre-surface treatment of the filler, it not only improves the viscosity reducing effect of the composite system (see Table 1), It also improves the mechanical strength of the resin-inorganic filler composite molded product. In particular, the improvement effect is remarkable in cured coating films by irradiation with active energy rays (see Tables 5 and 6).

The present invention provides a surface treatment agent that is effective in a wide range of combinations of resin-inorganic filler composite systems, particularly in photocurable resin-inorganic filler composite systems, and has extremely great industrial significance.

Claims (1)

[Claims] (1) A reaction product of tetraalkoxytitanium and/or a hydrolyzed condensation product (polymer) of tetraalkoxytitanium having an average degree of condensation of 6 or less and itaconic anhydride or itaconic acid half ester, which has 35 free substituents. ~
90% is RO- group (herein, R represents an alkyl group having 1 to 6 carbon atoms having a straight chain or side chain) and the remainder is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ group (here, R' is R
1 carbon number having a straight chain or side chain that is the same as or different from
~6 alkyl group. ) an alkoxytitanium-based surface treatment agent characterized by containing an alkoxytitanium derivative